Patent Application
20070059551
This application claims priority under 35 USC 119 from Japanese patent Application Nos. 2005-267556, 2005-267557, and 2006-047240, the disclosures of which are incorporated by reference herein.
1. Field of the Invention
The invention relates to a composition for an organic electroluminescent element, a method for manufacturing an organic electroluminescent element, and an organic electroluminescent element.
2. Description of the Related Art
Nowadays, research and developments concerning various display elements are actively conducted. Among them, an organic electroluminescent element (hereinafter occasionally referred to as “an organic EL element” or “a luminescent element”) attracts attention because the organic luminescent element enables high-luminance luminescence at low voltage. Because the organic EL element has advantages such as easier production and capability to form a thinner and lighter luminescent element compared to other luminescent elements, use as a thin display element has been researched and developed. In recent years, a high-performance organic EL element has been obtained which is comparable to a light-emitting diode (LED) even in respects of the luminance, the luminous efficiency, the durability, and the like. The organic EL element is promising particularly as an element that realizes a cheep and large area full-color display element.
In the production of organic EL elements, a thin film pattern, which is an organic compound layer (an organic layer) disposed between a pair of electrodes, can be formed by the vacuum deposition method, the spin coating method, the printing method, the ink jet method, and the like.
Organic layers of organic EL elements are typically manufactured by the deposition method. Japanese Patent Application Laid-Open (JP-A) Nos. 9-167684 and 2000-195665 have proposed methods in which an organic compound layer is uniformly formed on a temporary substrate of mica or a film in advance by the deposition method, then the substrate and the organic layer are brought into proximity, followed by heating and deposition. However, these methods have a problem in that the manufacturing efficiency is not good because the deposition method is used. Furthermore, because only a low molecular organic compound can be used for organic electroluminescence (EL) due to adoption of the deposition method, there is a problem in that the bending resistance and the durability of film strength and the like are insufficient when used in a flexible display and the like. The problem is apparent particularly when applied to a large area.
A polymer-type organic EL element that uses a luminescent thin film containing a low molecular compound dispersed in a binder resin, is also known. These polymer-type elements are advantageous also in making a large area display, and are expected to be applied to a flexible display. However, because the deposition method cannot be adapted for forming an organic luminescent thin film, the thin film is formed directly on the substrate by a wet process.
However, the wet process has problems in that the uniformity in the thickness of the organic thin film becomes insufficient due to the surface tension of the solution, and that each organic compound layer dissolves at the interface when organic layers are stacked. For this reason, the organic electroluminescent element obtained by this method has had a problem in that the luminous efficiency and the durability of the element are inferior.
The following International Publication No. WO 00/41893 pamphlet has proposed a thermal transfer method with a laser using a donor sheet having an organic thin film and a photothermal conversion layer. However, the thermal transfer as described in the literature has a problem in that the gas is entrapped at the adhesion interface of the organic layer and the element function is deteriorated. Furthermore, there is also a problem in that the luminous efficiency and durability of the organic EL element, and the uniformity of the luminescent surface vary depending on the condition of the interface of the organic layer.
Furthermore, when an organic thin film pattern is formed by a patterned thermal writing that uses a heating head and a laser used in the print technology field, the temperature distribution is generated on the periphery of the pattern by thermal diffusion property and the outline of the organic thin film pattern is not cut finely from the donor side. For this reason, there are problems in that the variation in the luminescent amount occurs, defects happen by electric failure and thin film fragments, and the durability is deteriorated. Furthermore, there is a problem of decrease in the yield caused by the malalignment of the substrate relative to the heating head or the laser.
The ink jet method has advantages such as ability to make highly accurate pattern, applicability to formation of a large area pattern, and capability of price reduction due to lack of necessity to use an expensive vacuum equipment. The ink jet method is particularly suitable for forming a polymer-based organic compound layer. Various methods for manufacturing the organic EL element involving the ink jet method have been disclosed (see, for example, Japanese Patent Application Laid Open (JP-A) Nos. 11-40358 and 11-54270, and the first pamphlet of International Publication No. WO 03/026359A1).
However, there is a problem in that the composition used in the manufacture of the organic EL element using the ink jet method has poor storability over time and that the composition may deteriorate when held in an ink jet device or the like for a long time. Manufacturing of the element using the deteriorated composition leads to the decrease in the element performance such as the luminous efficiency and the driving durability, and thus stable manufacture of the element is made difficult. A composition with excellent storability for an organic electroluminescent element has not been provided yet.
The method for manufacturing an organic EL element, which uses a transfer material to form the organic layer, has been proposed (for example, see JP-A No. 2004-79317). According to this manufacturing method, a luminescent element excellent in luminous efficiency, luminance, and durability can be easily manufactured by using a transfer material for forming the organic layer. However, there are needs for further improvement in the stability upon transfer of a transfer layer (an organic layer) from the transfer material to the substrate under heat or pressure, or in the stability of the transfer material over time.
The invention has been made in consideration of the above-mentioned situation, and provides a composition for an organic electroluminescent element, a method for manufacturing an organic electroluminescent element, and an organic electroluminescent element.
A first aspect of the invention is to provide a composition for an organic electroluminescent element capable of forming a pattern by an ink jet method, comprising at least one metal complex having a tridentate or higher-dentate ligand.
A second aspect of the invention is to provide a method for manufacturing an organic electroluminescent element, the method comprising forming a first electrode on a substrate, forming an organic compound layer by discharging the composition of the first aspect in a pattern onto the side of the substrate that has the first electrode thereon using an ink jet apparatus, and forming a second electrode on the organic compound layer.
A third aspect of the invention is to provide a method for manufacturing an organic electroluminescent element, the method comprising forming a first electrode on a substrate, superposing a transfer material having an organic compound layer containing a metal complex having a tridentate or higher-dentate ligand provided on a temporary support, on the side of the substrate that has the first electrode thereon, applying heat and/or pressure thereto, peeling away the temporary support so as to transfer the organic compound layer onto the side of the substrate that has the first electrode thereon, and forming a second electrode on the organic compound layer.
In the following, the invention will be described in detail.
[Composition for an Organic Electroluminescent Element]
The composition according to the invention for an organic electroluminescent element (hereinafter referred to as “composition for an organic EL element”) is a composition for an organic EL element capable of forming a pattern by an ink jet method, and contains at least one metal complex having a tridentate or higher-dentate ligand.
The metal complex having a tridentate or higher-dentate ligand in the invention is a metal complex excellent in stability in liquid.
Since the composition for an organic EL element according to the invention uses a metal complex having a tridentate of more ligand, the deterioration of the composition for an organic EL element with the passage of time can be effectively suppressed. An organic EL element that has high luminous efficiency, high luminance, and excellent durability can be manufactured stably and easily by applying this composition for an organic EL element to the manufacture of an organic EL element involving the ink jet method.
In the following, each component of the composition for an organic EL element according to the invention will be described.
[Metal Complex Having a Tridentate or Higher-Dentate Ligand]
First, the metal complex having a tridentate or higher-dentate ligand according to the invention will be described in detail.
In the metal complex according to the invention, the atoms coordinating to the metal ion are not particularly limited. An oxygen atom, a nitrogen atom, a carbon atom, a sulfur atom, or a phosphorus atom is preferable, an oxygen atom, a nitrogen atom, or a carbon atom is more preferable, and a nitrogen atom or a carbon atom is still more preferable.
The metal ion in the metal complex in the invention is not particularly limited. From the viewpoint of the improvement in the luminous efficiency, the improvement in durability and the decrease in the driving voltage, transition metal ions and rare-earth metal ions are preferable; an iridium ion, a platinum ion, a gold ion, a rhenium ion, a tungsten ion, a rhodium ion, a ruthenium ion, an osmium ion, a palladium ion, a silver ion, a copper ion, a cobalt ion, a zinc ion, a nickel ion, a lead ion, an aluminum ion, a gallium ion, and rare-earth metal ions (for example, an europium ion, a gadolinium ion, and a terbium ion) are more preferable; an iridium ion, a platinum ion, a gold ion, a rhenium ion, a tungsten ion, a palladium ion, a zinc ion, an aluminum ion, a gallium ion, an europium ion, a gadolinium ion, and a terbium ion are still more preferable. When the metal complex is used as a luminescent material, an iridium ion, a platinum ion, a rhenium ion, a tungsten ion, an europium ion, a gadolinium ion, and a terbium ion are particularly preferable.
When the metal complex in the invention is used as a charge transport material or a host material in a luminescent layer, an iridium ion, a platinum ion, a palladium ion, a zinc ion, an aluminum ion, and a gallium ion are particularly preferable.
As metal complexes having a tridentate or higher-dentate ligand in the invention, metal complexes having a ligand of tridentate to hexadentate are preferable from the viewpoint of the improvement in the luminous efficiency and the improvement in durability. In the case of metal ions which easily form a hexa-coordinate type complex, such as an iridium ion, metal complexes having a tridentate, a quadridentate, or a hexadentate ligand are preferable. In the case of metal ions which easily form a tetra-coordinate type complex, such as a platinum ion, metal complexes having a tridentate or a quadridentate ligand are more preferable, and metal complexes having a quadridentate ligand are still more preferable.
The ligand of the metal complex in the invention is preferably chain or circular from the viewpoint of the improvement in the luminous efficiency and the improvement in durability, and preferably has at least one nitrogen-containing heterocycle (for example, a pyridine ring, a quinoline ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, and a triazole ring) which coordinates to the center metal (for example, M11 in the case of a compound represented by the after-mentioned formula (I) with nitrogen. The nitrogen-containing heterocycle is preferably a nitrogen-containing six-membered heterocycle or a nitrogen-containing five-membered heterocycle. The heterocycles described above may form one or more condensed rings with other rings.
The expression “the ligand of a metal complex is chain” means that the ligand of the metal complex does not take a cyclic structure (for example, a terpyridyl ligand). Furthermore, the expression “the ligand of a metal complex is circular” means that plural ligands in the metal complex are bonded mutually to form a closed structure (for example, a phthalocyanine ligand or a crown ether ligand).
The metal complex in the invention is preferably a compounds represented by the formula (I), (II), or (III), which will be described in detail later.
The compound represented by Formula (I) will be described first.
In Formula (I), M11 represents a metal ion; L11 to L15 each independently represent a ligand coordinated to M11; in no case does an additional atomic group connect L11 and L14 to form a cyclic ligand; in no case, is L15 bonded to both L11 and L14 to form a cyclic ligand; Y11 to Y13 each independently represent a connecting group, a single bond, or a double bond; when Y11, Y12, or Y13 represent a connecting group, the bond between L11 and Y12, the bond between Y12 and L12, the bond between L12 and Y11, the bond between Y11 and L13, the bond between L13 and Y13, and the bond between Y13 and L14 are each independently a single bond or a double bond; and n11 represents an integer of 0 to 4. Each bond connecting M11 and each of L11 to L15 may be selected from a coordinate bond, an ionic bond and a covalent bond.
Hereinafter, details of the compound represented by Formula (I) will be described.
In Formula (I), M11 represents a metal ion. The metal ion is not particularly limited, but is preferably a divalent or trivalent metal ion. Preferable examples of the divalent or trivalent metal ion include a platinum ion, an iridium ion, a rhenium ion, a palladium ion, a rhodium ion, a ruthenium ion, a copper ion, a europium ion, a gadolinium ion, and a terbium ion. More preferable examples thereof include a platinum ion, an iridium ion, and a europium ion. Still more preferable examples thereof include a platinum ion and an iridium ion. Particularly preferable examples thereof include a platinum ion.
In Formula (I), L11, L12, L13, and L14 each independently represent a moiety coordinating to M11. Preferable examples of the atom coordinating to M11 contained in L11, L12, L13, or L14 include preferably a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom, and a phosphorus atom. More preferable examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, and a carbon atom. Still more preferable examples thereof include a nitrogen atom, an oxygen atom, and a carbon atom.
The bonds between M11 and L11, between M11 and L12, between M11 and L13, between M11 and L14 each may be independently selected from a covalent bond, an ionic bond, and a coordination bond. In this specification, the terms “ligand” and “coordinate” are used also when the bond between the central metal and the ligand is a bond (an ionic bond or a covalent bond) other than a coordination bond, as well as when the bond between the central metal and the ligand is a coordination bond, for convenience of the explanation.
The entire ligand comprising L11, Y12, L12, Y11, L13, Y13, and L14 is preferably an anionic ligand. The term “anionic ligand” used herein refers to a ligand having at least one anion bonded to the metal. The number of anions in the anionic ligand is preferably 1 to 3, more preferably from 1 or 2, and still more preferably 2.
When the moiety represented by any of L11, L12, L13, and L14 coordinates to M11 via a carbon atom, the moiety is not particularly limited, and examples thereof include imino ligands, aromatic carbon ring ligands (e.g., a benzene ligand, a naphthalene ligand, an anthracene ligand, and a phenanthrene ligand), and heterocyclic ligands [e.g., a thiophene ligand, a pyridine ligand, a pyrazine ligand, a pyrimidine ligand, a thiazole ligand, an oxazole ligand, a pyrrole ligand, an imidazole ligand, and a pyrazole ligand, ring-condensation products thereof (e.g., a quinoline ligand and a benzothiazole ligand), and tautomers thereof].
When the moiety represented by any of L11, L12, L13, and L14 coordinates to M11 via a nitrogen atom, the moiety is not particularly limited, and examples thereof include nitrogen-containing heterocyclic ligands such as a pyridine ligand, a pyrazine ligand, a pyrimidine ligand, a pyridazine ligand, a triazine ligand, a thiazole ligand, an oxazole ligand, a pyrrole ligand, an imidazole ligand, a pyrazole ligand, a triazole ligand, an oxadiazole ligand, and a thiadiazole ligand, and ring-condensation products thereof (e.g., a quinoline ligand, a benzoxazole ligand, and a benzimidazole ligand), and tautomers thereof [in the invention, the following ligands (pyrrole tautomers) are also included in tautomers, in addition to normal isomers: the five-membered heterocyclic ligand of compound (24), the terminal five-membered heterocyclic ligand of compound (64), and the five-membered heterocycle ligand of compound (145), the compounds (24), (64), (145) being shown below as typical examples of the compound represented by formula (I)]; amino ligands such as alkylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as methylamino), arylamino ligands (e.g., and phenylamino), acylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetylamino and benzoylamino), alkoxycarbonylamino ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino ligands (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), and imino ligands. These ligands may be substituted.
When the moiety represented by any of L11, L12, L13, and L14 coordinates to M11 via an oxygen atom, the moiety is not particularly limited, and examples thereof include alkoxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, and 2-ethylhexyloxy), aryloxy ligands (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, and 2-naphthyloxy), heterocyclic oxy ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, and quinolyloxy), acyloxy ligands (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), silyloxy ligands (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy and triphenylsilyloxy), carbonyl ligands (e.g., ketone ligands, ester ligands, and amido ligands), and ether ligands (e.g., dialkylether ligands, diarylether ligands, and furyl ligands).
When the moiety represented by any of L11, L12, L13, and L14 coordinates to M11 via a sulfur atom, the moiety is not particularly limited, and examples thereof include alkylthio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), arylthio ligands (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenylthio), heterocyclic thio ligands (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, and 2-benzothiazolylthio), thiocarbonyl ligands (e.g., thioketone ligands and thioester ligands), and thioether ligands (e.g., dialkylthioether ligands, diarylthioether ligands, and thiofuryl ligands). These substitution ligands may respectively have a substitutent.
When the moiety represented by any of L11, L12, L13, and L14 coordinates to M11 via a phosphorus atom, the moiety is not particularly limited, and examples thereof include dialkylphosphino groups, diarylphosphino groups, trialkylphosphine groups, triarylphosphine groups, phosphinine groups and the like. These groups each may have a substituent.
In a preferable embodiment, L11 and L14 each independently represent a moiety selected from an aromatic carbon ring ligand, an alkyloxy ligand, an aryloxy ligand, an ether ligand, an alkylthio ligand, an arylthio ligand, an alkylamino ligand, an arylamino ligand, an acylamino ligand, or a nitrogen-containing heterocyclic ligand [e.g., a pyridine ligand, a pyrazine ligand, a pyrimidine ligand, a pyridazine ligand, a triazine ligand, a thiazole ligand, an oxazole ligand, a pyrrole ligand, an imidazole ligand, a pyrazole ligand, a triazole ligand, an oxadiazole ligand, a thiadiazole ligand, or a condensed ring ligand containing one or more of the above ligands (e.g., a quinoline ligand, a benzoxazole ligand, or a benzimidazole ligand), or a tautomer of any of the above ligands]; more preferably, an aromatic carbon ring ligand, an aryloxy ligand, an arylthio ligand, an arylamino ligand, a pyridine ligand, a pyrazine ligand, an imidazole ligand, a condensed ring ligand containing one or more of the above ligands (e.g., a quinoline ligand, a quinoxaline ligand, or a benzimidazole ligand), or a tautomer of any of the above ligands; still more preferably, an aromatic carbon ring ligand or an aryloxy ligand, an arylthio ligand, or an arylamino ligand; and particularly preferably, an aromatic carbon ring ligand or an aryloxy ligand.
In a preferable embodiment, L12 and L13 each independently represent a moiety forming a coordination bond with M11. The moiety forming a coordination bond with M11 is preferably a pyridine, pyrazine, pyrimidine, triazine, thiazole, oxazole, pyrrole or triazole ring, a condensed ring containing one or more of the above rings (e.g., a quinoline ring, a benzoxazole ring, a benzimidazole ring, an indolenine ring), or a tautomer of any of the above rings; more preferably a pyridine, pyrazine, pyrimidine, or pyrrole ring, a condensed ring containing one or more of the above rings (e.g., a quinoline ring, a benzopyrrole ring), or a tautomer of any of the above rings; still more preferably a pyridine, pyrazine or pyrimidine ring, or a condensed ring containing one or more of the above rings (e.g., quinoline ring); particularly preferably a pyridine ring or a condensed ring containing a pyridine ring (e.g., a quinoline ring).
In Formula (I), L15 represents a ligand coordinating to M11. L15 is preferably a monodentate to tetradentate ligand and more preferably a monodentate to tetradentate anionic ligand. The monodentate to tetradentate anionic ligand is not particularly limited, but is preferably a halogen ligand, a 1,3-diketone ligand (e.g., an acetylacetone ligand), a monoanionic bidentate ligand containing a pyridine ligand [e.g., a picolinic acid ligand or a 2-(2-hydroxyphenyl)-pyridine ligand], or a tetradentate ligand L11, Y12, L12, Y11, L13, Y13, and L14 can form; more preferably, a 1,3-diketone ligand (e.g., an acetylacetone ligand), a monoanionic bidentate ligand containing a pyridine ligand [e.g., a picolinic acid ligand or a 2-(2-hydroxyphenyl)-pyridine ligand], or a tetradentate ligand L11, Y12, L12, Y11, L13, Y13, and L14 can form; still more preferably, a 1,3-diketone ligand (e.g., an acetylacetone ligand) or a monoanionic bidentate ligand containing a pyridine ligand [e.g., a picolinic acid ligand or a 2-(2-hydroxyphenyl)-pyridine ligand); and particularly preferably, a 1,3-diketone ligand (e.g., an acetylacetone ligand). The number of coordination sites and the number of ligands do not exceed the valency of the metal. L15 does not bind to both L11 and L14 to form a cyclic ligand.
In Formula (I), Y11, Y12 and Y13 each independently represent a connecting group or a single or double bond. The connecting group is not particularly limited, and preferable examples thereof include connecting groups containing atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, and phosphorus atoms. Specific examples of such connecting groups include the following groups:
When Y11 is a connecting group, the bond between L12 and Y11 and the bond between Y11 and L13 are each independently a single or double bond. When Y12 is a connecting group, the bond between L11 and Y12 and the bond between Y12 and L12 are each independently a single or double bond. When Y13 is a connecting group, the bond between L13 and Y13 and the bond between Y13 and L14 are each independently a single or double bond.
Preferably, Y11, Y12, and Y13 each independently represent a single bond, a double bond, a carbonyl connecting group, an alkylene connecting group, or an alkenylene group. Y11 is more preferably a single bond or an alkylene group, and still more preferably an alkylene group. Each of Y12 and Y13 is more preferably a single bond or an alkenylene group and still more preferably a single bond.
The ring formed by Y12, L11, L12, and M11, the ring formed by Y11, L12, L13, and M11, and the ring formed by Y13, L13, L14, and M11 are each preferably a four- to ten-membered ring, more preferably a five- to seven-membered ring, and still more preferably a five- to six-membered ring.
In Formula (I), n11 represents an integer of 0 to 4. When M11 is a tetravalent metal, n11 is 0. When M11 is a hexavalent metal, n11 is preferably 1 or 2 and more preferably 1. When M11 is a hexavalent metal and n11 is 1, L15 represents a bidentate ligand. When M11 is a hexavalent metal and n11 is 2, L15 represents a monodentate ligand. When M11 is an octavalent metal, n11 is preferably from 1 to 4, more preferably, 1 or 2, and still more preferably 1. When M11 is an octavalent metal and n11 is 1, L15 represents a tetradentate ligand. When M11 is an octavalent metal and n11 is 2, L15 represents a bidentate ligand. When n11 is two or greater, there are plural L15's, and the L15's may be the same as or different from each other.
Preferable embodiments of the compound represented by Formula (I) include compounds represented by the following Formulae (1), (2), (3) or (4).
Firstly, explanation of the compound represented by Formula (1) is provided.
In Formula (1), M21 represents a metal ion; and Y21 represents a connecting group or a single or double bond. Y23 and Y23 each represent a single bond or a connecting group. Q21 and Q22 each represent an atomic group forming a nitrogen-containing heterocycle, and the bond between Y21 and the ring containing Q21 and the bond between Y21 and the ring containing Q22 are each a single or double bond. X21 and X22 each independently represent an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom. R21, R22, R23, and R24 each independently represent a hydrogen atom or a substituent. R21 and R22 may bind to each other to form a ring, and R23 and R24 may bind to each other to form a ring. L25 represents a ligand coordinating to M21, and n21 represents an integer of 0 to 4.
The compound represented by formula (1) will be described in detail.
In Formula (1), the definition of M21 is the same as the definition of M11 in Formula (I), and their preferable ranges are also the same.
Q21 and Q22 each independently represent an atomic group forming a nitrogen-containing heterocycle (ring containing a nitrogen atom coordinating to M21). The nitrogen-containing heterocycles formed by Q21 and Q22 are not particularly limited, and may be selected, for example, from a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a thiazole ring, an oxazole ring, a pyrrole ring, and a triazole ring, and condensed rings containing one or more of the above rings (e.g., a quinoline ring, a benzoxazole ring, a benzimidazole ring, and an indolenine ring), and tautomers thereof.
The nitrogen-containing heterocycle formed by Q21 or Q22 is preferably selected from a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrazol ring, an imidazol ring, an oxazol ring, a pyrrol ring, a benzazol ring, and condensed rings containing one or more of the above rings (e.g., a quinoline ring, a benzoxazole ring, a benzimidazole ring, and an indolenine ring), and tautomers thereof, more preferably selected from a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazol ring, a pyrrol ring, and condensed rings containing one or more of the above rings (e.g., a quinoline ring), and tautomers thereof, still more preferably a pyridine ring, or a condensed ring containing the pyridine ring (e.g., a quinoline ring), and particularly preferably a pyridine ring.
X21 and X22 each independently represent an oxygen atom, a sulfur atom, or a substituted or unsubstituted nitrogen atom. X21 and X22 are each preferably an oxygen atom, a sulfur atom, or a substituted nitrogen atom, more preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
The definition of Y21 is the same as that of Y11 in Formula (I), and their preferable ranges are also the same.
Y22 and Y23 each independently represent a single bond or a connecting group, preferably a single bond. The connecting group is not particularly limited, and examples thereof include a carbonyl connecting group, a thiocarbonyl connecting group, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, connecting groups which connects moieties via an oxygen atom, connecting groups which connects moieties via a nitrogen atom, and connecting groups comprising combinations of connecting groups selected from the above.
The connecting group represented by Y22 or Y23 is preferably a carbonyl connecting group, an alkylene connecting group, or an alkenylene connecting group, more preferably a carbonyl connecting group or an alkenylene connecting group, and still more preferably a carbonyl connecting group.
R21, R22, R23, and R24 each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include alkyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include a propargyl group and a 3-pentynyl group), aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, a naphthyl group, and an anthranyl group), amino groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms, and examples thereof include an amino group, a, methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, and a ditolylamino group),
alkoxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, a ethoxy group, a butoxy group, and a 2-ethylhexyloxy group), aryloxy groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group), heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, and a quinolyloxy group), acyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group), aryloxycarbonyl groups (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonyl group),
acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group), acylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group), alkoxycarbonylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group), aryloxycarbonylamino groups (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group), sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group), sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group),
carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group), alkylthio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group), arylthio groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group), heterocyclic thio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a pyridylthio group, a 2-benzimidazolylthio group, a 2-benzoxazolylthio group, and a 2-benzothiazolylthio group), sulfonyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group), sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group), ureido groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a ureido group, a methylureido group, and a phenylureido group),
phosphoric amide groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a diethylphosphoric amide group and a phenylphosphoric amide group), a hydroxy group, a mercapto group, halogen atoms (such as fluorine, chlorine, bromine, or iodine), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino groups, hydrazino groups, imino groups, heterocyclic groups (preferably having 1 to 30 carbon atoms and more preferably 1 to 12 carbon atoms; the heteroatom(s) may be selected from nitrogen, oxygen, and sulfur atoms), and examples thereof include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a carbazolyl group, and an azepinyl group), silyl groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group), and silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy group). These substituents may have a substitutent(s).
In a preferable embodiment, R21, R22, R23, and R24 are each independently selected from alkyl groups or aryl groups. In another preferable embodiment, R21 and R22 are groups that bind to each other to form a ring structure (e.g., a benzo-condensed ring or a pyridine-condensed ring), and/or R23 and R24 are groups that bind to each other to form a ring structure or ring structures (e.g., a benzo-condensed ring or a pyridine-condensed ring). In a more preferable embodiment, R21 and R22 are groups that bind to each other to form a ring structure (e.g., a benzo-condensed ring or a pyridine-condensed ring), and/or R23 and R24 are groups that bind to each other to form a ring structure or ring structures (e.g., a benzo-condensed ring or a pyridine-condensed ring).
The definition of L25 is the same as that of L15 in Formula (I), and their preferable ranges are also the same.
The definition of n21 is the same as that of n11 in Formula (I), and their preferable ranges are also the same.
In Formula (1), examples of preferable embodiments are described below:
(1) the rings formed by Q21 and Q22 are pyridine rings, and Y21 is a connecting group;
(2) the rings formed by Q21 and Q22 are pyridine rings, Y21 is a single or double bond, and X21 and X22 are selected from sulfur atoms, substituted nitrogen atoms, and unsubstituted nitrogen atom;
(3) the rings formed by Q21 and Q22 are each a five-membered nitrogen-containing heterocycle, or a nitrogen-containing six-membered ring containing two or more nitrogen atoms.
Preferable examples of compounds represented by Formula (1) are compounds represented by the following Formula (I-A).
The compound represented by Formula (I-A) will be described below.
In Formula (I-A), the definition of M31 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
Z31, Z32, Z33, Z34, Z35, and Z36 each independently represent a substituted or unsubstituted carbon or nitrogen atom, and preferably a substituted or unsubstituted carbon atom. The substituent on the carbon may be selected from the substituents described as examples of R21 in Formula (1). Z31 and Z32 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z32 and Z33 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z33 and Z34 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z34 and Z35 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z35 and Z36 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z31 and T31 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z36 and T38 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring).
The substituent on the carbon is preferably an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group capable of forming a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring), or a halogen atom, more preferably an alkylamino group, an aryl group, or a group capable of forming a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring), still more preferably an aryl group or a group capable of forming a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring), and particularly preferably a group capable of forming a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring).
T31, T32, T33, T34, T35, T36, T37, and T38 each independently represent a substituted or unsubstituted carbon or nitrogen atom, and more preferably a substituted or unsubstituted carbon atom. Examples of the substituents on the carbon include the groups described as examples of R21 in formula (1); T31 and T32 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring). T32 and T33 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring). T33 and T34 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring). T35 and T36 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring). T36 and T37 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring). T37 and T38 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring).
The substituent on the carbon is preferably an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group capable of forming a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring), or a halogen atom; more preferably an aryl group, a group capable of forming a condensed ring (e.g., a benzo-condensed ring or pyridine-condensed ring), or a halogen atom; still more preferably an aryl group or a halogen atom, and particularly preferably an aryl group.
The definitions and preferable ranges of X31 and X32 are the same as the definitions and preferable ranges of X21 and X22 in Formula (1), respectively.
The compound represented by Formula (2) will be described below.
In Formula (2), the definition of M51 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
The definitions of Q51 and Q52 are the same as the definitions of Q21 and Q22 in Formula (1), and their preferable ranges are also the same.
Q53 and Q54 each independently represent a group forming a nitrogen-containing heterocycle (ring containing a nitrogen atom coordinating to M51). The nitrogen-containing heterocycles formed by Q53 and Q54 are not particularly limited, and are preferably selected from tautomers of pyrrole compounds, tautomers of imidazole compounds (e.g., the five-membered heterocyclic ligand contained in the compound (29) shown below as a specific example of the compound represented by Formula (I)), tautomers of thiazole compounds (e.g., the five-membered heterocyclic ligand contained in the compound (30) shown below as a specific example of the compound represented by Formula (I)), and tautomers of oxazole compounds (e.g., the five-membered heterocyclic ligand contained in the compound (31) shown below as a specific example of the compound represented by Formula (I)), more preferably selected from tautomers of pyrrole, imidazole, and thiazole compounds; still more preferably selected from tautomers of pyrrole and imidazole compounds; and particularly preferably selected from tautomers of pyrrole compounds.
The definition of Y51 is the same as that of Y11 in Formula (I), and their preferable range are also the same.
The definition of L55 is the same as that of L15 in Formula (I), and their preferable ranges are also the same.
The definition of n51 is the same as that of n11, and their preferable ranges are also the same.
W51 and W52 each independently represent a substituted or unsubstituted carbon or nitrogen atom, more preferably an unsubstituted carbon or nitrogen atom, and still more preferably an unsubstituted carbon atom.
The compound represented by Formula (3) will be described below.
In Formula (3), the definitions and preferable ranges of MA1, QA1, QA2, YA1, YA2, YA3, RA1, RA2, RA3, RA4, LA5, and nA1 are the same as the definitions and preferable ranges of M21, Q21, Q22, Y21, Y22, Y23, R21, R22, R23, R24, L25 and n21 in Formula (1) respectively.
Preferable examples of compounds represented by Formula (3) are compounds represented by the following Formula (3-A) or (3-B).
The compound represented by Formula (3-A) will be described first.
In Formula (3-A), the definitions of M61 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
Q61 and Q62 each independently represent a ring-forming group. The rings formed by Q61 and Q62 are not particularly limited, and examples thereof include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a thiophene ring, an isothiazole ring, a furan ring, an isoxazole ring, and condensed rings thereof.
Each of the rings formed by Q61 and Q62 is preferably a benzene ring, a pyridine ring, a thiophene ring, a thiazole ring, or a condensed ring containing one or more of the above rings; more preferably a benzene ring, a pyridine ring, or a condensed ring containing one or more of the above rings; and still more preferably a benzene ring or a condensed ring containing a benzene ring.
The definition of Y61 is the same as that of Y11 in Formula (I), and their preferable ranges are also the same.
Y62 and Y63 each independently represent a connecting group or a single bond. The connecting group is not particularly limited, and examples thereof include a carbonyl connecting group, a thiocarbonyl connecting group, alkylene groups, alkenylene groups, arylene groups, heteroarylene groups, a connecting group which connects moieties via an oxygen or nitrogen atom, and connecting groups comprising combinations of connecting groups selected from the above.
Y62 and Y63 are each independently selected, preferably from a single bond, a carbonyl connecting group, an alkylene connecting group, and an alkenylene group, more preferably from a single bond and an alkenylene group, and still more preferably from a single bond.
The definition of L65 is the same as that of L15 in Formula (I), and their preferable ranges are also the same.
The definition of n61 is the same as the definition of n11 in Formula (I), and their preferable ranges are also the same.
Z61, Z62, Z63, Z64, Z65, Z66, Z67, and Z68 each independently represent a substituted or unsubstituted carbon or nitrogen atom, and preferably a substituted or unsubstituted carbon atom. Examples of the substituent on the carbon include the groups described as examples of R21 in Formula (1). Z61 and Z62 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring) Z62 and Z63 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z63 and Z64 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z65 and Z66 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z66 and Z67 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). Z67 and Z68 may be bonded to each other via a connecting group to form a condensed ring (e.g., a benzo-condensed ring or a pyridine-condensed ring). The ring formed by Q61 may be bonded to Z61 via a connecting group to form a ring. The ring formed by Q62 may be bonded to Z68 via a connecting group to form a ring.
The substituent on the carbon is preferably an alkyl group, an alkoxy group, an alkylamino group, an aryl group, a group capable of forming a condensed ring (e.g., benzo-condensed ring or pyridine-condensed ring), or a halogen atom, more preferably an alkylamino group, an aryl group, or a group capable of forming a condensed ring (e.g., benzo-condensed ring or pyridine-condensed ring), still more preferably an aryl group or a group capable of forming a condensed ring (e.g., benzo-condensed ring or pyridine-condensed ring), and particularly preferably a group capable of forming a condensed ring (e.g., benzo-condensed ring or pyridine-condensed ring).
The compound represented by Formula (3-B) will be described below.
In Formula (3-B), the definition of M71 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
The definitions and preferable ranges of Y71, Y72, and Y73 are the same as the definition and preferable range of Y62 in Formula (3-A).
The definition of L75 is the same as that of L15 in Formula (I), and their preferable ranges are also the same.
The definition of n71 is the same as that of n11 in Formula (I), and their preferable ranges are also the same.
Z71, Z72, Z73, Z74, Z75, and Z76 each independently represent a substituted or unsubstituted carbon or nitrogen atom, and more preferably a substituted or unsubstituted carbon atom. Examples of the substituent on the carbon include the groups described as examples of R21 in Formula (1). In addition, Z71 and Z72 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring). Z72 and Z73 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring). Z73 and Z74 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring). Z74 and Z75 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring). Z75 and Z76 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring). The definitions and preferable ranges of R71 to R74 are the same as the definitions of R21 to R24 in Formula (1), respectively. R71 and R72 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring or a pyridine ring). R73 and R74 may be bonded to each other via a connecting group to form a ring (e.g., a benzene ring or a pyridine ring).
Preferable examples of compounds represented by Formula (3-B) include compounds represented by the following formula (3-C).
The compound represented by Formula (3-C) will be described below.
In Formula (3-C), RC1 and RC2 each independently represent a hydrogen atom or a substituent, and the substituents may be selected from the alkyl groups and aryl groups described as examples of R21 to R24 in Formula (1). RC3, RC4, RC5, and RC6 each independently represent a hydrogen atom or a substituent, and the substituent may be selected from the substituents described as examples of R21 to R24 in Formula (1). Each of nC3 and nC6 represents an integer of 0 to 3; each of nC4 and nC5 represents an integer of 0 to 4; when there are plural RC3s, RC4s, RC5s, or RC6s, the plural RC3s, RC4s, RC5s, or RC6 s may be the same as each other or different from each other, and may be bonded to each other to form a ring. RC3, RC4, RC5, and RC6 each preferably represent an alkyl group, an aryl group, a heteroaryl group, or a halogen atom.
The compound represented by Formula (4) will be described below.
In Formula (4), the definitions and preferable ranges of MB1, YB2, YB3, RB1, RB2, RB3, RB4, LB5, nB3, XB1, and XB2 are the same as the definitions of M21, Y22, Y23, R21, R22, R23, R24, L25, n21, X21, and X22 in Formula (1), respectively.
YB1 represents a connecting group whose definition is the same as that of Y21 in Formula (1). YB1 is preferably a vinyl group substituted at 1- or 2-position, a phenylene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or an alkylene group having 2 to 8 carbons.
RB5 and RB6 each independently represent a hydrogen atom or a substituent, and the substituent may be selected from the alkyl groups, aryl groups, and heterocyclic groups described as examples of R21 to R24 in Formula (1). However, YB1 is not bonded to RB5 or RB6. nB1 and nB2 each independently represent an integer of 0 or 1.
Preferable examples of the compound represented by Formula (4) include compounds represented by the following Formula (4-A).
The compound represented by Formula (4-A) will be described below.
In Formula (4-A), RD3 and RD4 each independently represent a hydrogen atom or a substituent, and RD1 and RD2 each represent a substituent. The substituents represented by RD1, RD2, RD3, and RD4 may be selected from the substituents described as examples of RB5 and RB6 in Formula (4), and have the same preferable range as RB5 and RB6 in Formula (4). nD1 and nD2 each represent an integer of 0 to 4. When there are plural RD1s, the plural RD1s may be the same as or different from each other or may be bonded to each other to form a ring. When there are plural RD2s, the plural RD2s may be the same as or different from each other or may be bonded to each other to form a ring. YD1 represents a vinyl group substituted at 1- or 2-position, a phenylene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, or an alkylene group having 1 to 8 carbon atoms.
Preferable examples of the metal complex having a tridentate ligand according to the invention include compounds represented by the following Formula (5).
The compound represented by Formula (5) will be described below.
In Formula (5), the definition of M81 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
The definitions and preferable ranges of L81, L82, and L83 are the same as the definitions and preferable ranges of L11, L12, and L13 in Formula (I), respectively.
The definitions and preferable ranges of Y81 and Y82 are the same as the definitions and preferable ranges of Y11 and Y12 in Formula (I), respectively.
L85 represents a ligand coordinating to M81. L85 is preferably a mono- to tri-dentate ligand and more preferably a monodentate to tridentate anionic ligand. The mono- to tri-dentate anionic ligand is not particularly limited, but is preferably a halogen ligand or a tridentate ligand L81, Y81, L82, Y82, and L83 can form, and more preferably a tridentate ligand L81, Y81, L82, Y82, and L83 can form. L85 is not directly bonded to L81 or L83. The numbers of coordination sites and ligands do not exceed the valency of the metal.
n81 represents an integer of 0 to 5. When M81 is a tetravalent metal, n81 is 1, and L85 represents a monodentate ligand. When M81 is a hexavalent metal, n81 is preferably from 1 to 3, more preferably 1 or 3, and still more preferably 1. When M81 is hexavalent and n81 is 1, L85 represents a tridentate ligand. When M81 is hexavalent and n81 is 2, L85 represents a monodentate ligand and a bidentate ligand. When M81 is hexavalent and n81 is 3, L85 represents a monodentate ligand. When M81 is an octavalent metal, n81 is preferably from 1 to 5, more preferably 1 or 2, and still more preferably 1. When M81 is octavalent and n81 is 1, L85 represents a pentadentate ligand. When M81 is octavalent and n81 is 2, L85 represents a tridentate ligand and a bidentate ligand. When M81 is octavalent and n81 is 3, L85 represents a tridentate ligand and two monodentate ligands, or represents two bidentate ligands and one monodentate ligand. When M81 is octavalent and n81 is 4, L85 represents one bidentate ligand and three monodentate ligands. When M81 is octavalent and n81 is 5, L85 represents five monodentate ligands. When n81 is two or greater, there are plural L85s, and the plural L85s may be the same as or different from each other.
In a preferable example of the compound represented by Formula (5), L81, L82, or L83 each represent an aromatic carbon ring containing a carbon atom coordinating to M81, a heterocycle containing a carbon atom coordinating to M81, or a nitrogen-containing heterocycle containing a nitrogen atom coordinating to M81, wherein at least one of L81, L82, and L83 is a nitrogen-containing heterocycle. Examples of the aromatic carbon ring containing a carbon atom coordinating to M81, heterocycle containing a carbon atom coordinating to M81, or nitrogen-containing heterocycle containing a nitrogen atom coordinating to M81 include the examples of ligands (moieties) each containing a nitrogen or carbon atom coordinating to M11 in Formula (I) described in the explanation of Formula (I). Preferable examples thereof are the same as in the description of ligands (moieties) each containing a nitrogen or carbon atom coordinating to M11 in Formula (I). Y81 and Y82 each preferably represent a single bond or a methylene group.
Other preferable examples of compounds represented by Formula (5) include compounds represented by the following Formulae (5-A) and (5-B).
The compound represented by Formula (5-A) will be described below.
In Formula (5-A), the definition of M91 is the same as that of M81 in Formula (5), and their preferable ranges are also the same.
Q91 and Q92 each represent a group forming a nitrogen-containing heterocycle (ring containing a nitrogen atom coordinating to M91). The nitrogen-containing heterocycles formed by Q91 and Q92 are not particularly limited, and examples thereof include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a thiazole ring, an oxazole ring, a pyrrole ring, a pyrazole ring, a imidazole, a triazole ring, and condensed rings containing one or more of the above rings (e.g., a quinoline ring, a benzoxazole ring, a benzimidazole ring, and an indolenine ring), and tautomers thereof.
Each of the nitrogen-containing heterocycles formed by Q91 and Q92 is preferably a pyridine ring, a pyrazole ring, a thiazole ring, an imidazole ring, a pyrrole ring, a condensed ring containing one or more of the above ring (e.g., a quinoline ring, a benzothiazole ring, a benzimidazole ring, or an indolenine ring), or a tautomer of any of the above rings; more preferably a pyridine ring, a pyrrole ring, a condensed ring containing one or more of these rings (e.g., a quinoline ring), or a tautomer of any of the above rings; still more preferably a pyridine ring or a condensed ring containing a pyridine ring (e.g., a quinoline ring); and particularly preferably a pyridine ring.
Q93 represents a group forming a nitrogen-containing heterocycle (ring containing a nitrogen atom coordinating to M91). The nitrogen-containing heterocycle formed by Q93 is not particularly limited, but is preferably a pyrrole ring, an imidazole ring, a tautomer of a triazole ring, or a condensed ring containing one or more of the above rings (e.g., benzopyrrole), and more preferably a tautomer of a pyrrole ring or a tautomer of a condensed ring containing a pyrrole ring (e.g., benzopyrrole).
The definitions and preferable ranges of W91 and W92 are the same as the definitions and preferable ranges of W51 and W52 in Formula (2), respectively.
The definition of L95 is the same as that of L85 in Formula (5), and their preferable ranges are also the same.
The definition of n91 is the same as that of n81 in Formula (5), and their preferable ranges are also the same.
The compound represented by Formula (5-B) will be described next.
In Formula (5-B), the definition of M101 is the same as that of M81 in Formula (5), and their preferable ranges are also the same.
The definition of Q102 is the same as that of Q21 in Formula (1), and their preferable ranges are also the same.
The definition of Q101 is the same as that of Q91 in Formula (5-A), and their preferable ranges are also the same.
Q103 represents a group forming an aromatic ring. The aromatic ring formed by Q103 is not particularly limited, but is preferably a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, or a condensed ring containing one or more of the above rings (e.g., a naphthalene ring), more preferably a benzene ring or a condensed ring containing a benzene ring (e.g., naphthalene ring), and particularly preferably a benzene ring.
The definitions and preferable ranges of Y101 and Y102 are the same as the definition and preferable range of Y22 in Formula (1).
The definition of L105 is the same as that of L85 in Formula (5), and their preferable ranges are also the same.
The definition of n101 is the same as that of n81 in Formula (5), and their preferable ranges are also the same.
The definition of X101 is the same as that of X21 in Formula (1), and their preferable ranges are also the same.
Another preferable embodiment of the metal complex containing a tridentate ligand according to the invention is a compound represented by Formula (II) shown below.
In Formula (II), MX1 represents a metal ion. QX11 to QX16 each independently represent an atom coordinating to MX1 or an atomic group containing an atom coordinating to MX1. LX11 to LX14 each independently represent a single bond, a double bond or a connecting group.
Namely, in Formula (II), the atomic group comprising QX11-LX11-QX12-LX12-QX13 and the atomic group comprising QX14-LX13-QX15-LX14-QX16 each form a tridentate ligand.
In addition, each of the bond between MX1 and each of QX11 to QX16 may be a coordination bond, an ionic bond, or a covalent bond.
The compound represented by Formula (II) will be described in detail below.
In Formula (II), MX1 represents a metal ion. The metal ion is not particularly limited, but is preferably a monovalent to trivalent metal ion, more preferably a divalent or trivalent metal ion, and still more preferably a trivalent metal ion. Specifically, a platinum ion, an iridium ion, a rhenium ion, a palladium ion, a rhodium ion, a ruthenium ion, a copper ion, a europium ion, a gadolinium, and a terbium ion are preferable. Among these, an iridium ion and a europium ion are more preferable, and an iridium ion is still more preferable.
QX11 to QX16 each represent an atom coordinating to MX1 or an atomic group containing an atom coordinating to MX1.
When any of QX11 to QX16 is an atom coordinating to MX1, specific examples of the atom include a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, and a sulfur atom. Preferable specific examples of the atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. More preferable specific examples of the atom include a nitrogen atom and an oxygen atom.
When any of QX11 to QX16 is an atomic group containing a carbon atom coordinating to MX1, examples of the atomic group coordinating to MX1 via a carbon atom include imino groups, aromatic hydrocarbon ring groups (such as a benzene ring group or a naphthalene ring group), heterocyclic groups (such as a thiophene group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group, a triazine group, a thiazole group, an oxazole group, a pyrrole group, an imidazole group, a pyrazole group, or a triazole group), condensed rings containing one or more of the above rings, and tautomers thereof.
When any of QX11 to QX16 is an atomic group containing a nitrogen atom coordinating to MX1, examples of the atomic group coordinating to MX1 via a nitrogen atom include nitrogen-containing heterocyclic groups, amino groups, and imino groups. Examples of the nitrogen-containing heterocyclic groups include pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazole, oxazole, pyrrole, imidazole, pyrazole, or triazole. Examples of the amino groups include alkylamino groups [preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include a methylamino group), arylamino groups (e.g., a phenylamino group)], acylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetylamino group and a benzoylamino group), alkoxycarbonylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group), aryloxycarbonylamino groups (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group), and sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino and benzenesulfonylamino group). These groups may have a substitutent(s).
When any of QX11 to QX16 is an atomic group containing an oxygen atom coordinating to MX1, examples of the atomic groups coordinating to MX1 via an oxygen atom include alkoxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, and a 2-ethylhexyloxy group), aryloxy groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group), heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, and a quinolyloxy group), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group), silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy), carbonyl groups (e.g., ketone groups, ester groups, and amido groups), and ether groups (e.g., dialkylether groups, diarylether groups, and furyl groups).
When any of QX11 to QX16 is an atomic group containing a silicon atom coordinating to MX1, examples of the atomic group coordinating to MX1 via a silicon atom include alkylsilyl groups (preferably having 3 to 30 carbon atoms, and examples thereof include a trimethylsilyl group), and arylsilyl groups (preferably, having 18 to 30 carbon atoms, and examples thereof include a triphenylsilyl group). These groups may have a substituent(s).
When any of QX11 to QX16 is an atomic group containing a sulfur atom coordinating to MX1, examples of the atomic group coordinating to MX1 via a sulfur atom include alkylthio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group), arylthio groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include a phenylthio group), heterocyclic thio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a pyridylthio group, a 2-benzimidazolylthio group, a 2-benzoxazolylthio group, and a 2-benzothiazolylthio group), thiocarbonyl groups (e.g., a thioketone group and a thioester group), and thioether groups (e.g., a dialkylthioether group, a diarylthioether group, and a thiofuryl group).
When any of QX11 to QX16 is an atomic group containing a phosphorus atom coordinating to MX1, examples of the atomic group coordinating to MX1 via a phosphorus atom include dialkylphosphino groups, diarylphosphino groups, trialkyl phosphines, triaryl phosphines, and phosphinine groups. These groups may have a substituent(s).
The atomic groups represented by QX11 to QX16 are each preferably an aromatic hydrocarbon ring group containing a carbon atom coordinating to MX1, an aromatic heterocyclic group containing a carbon atom coordinating to MX1, a nitrogen-containing aromatic heterocyclic group containing a nitrogen atom coordinating to MX1, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, or an dialkylphosphino group, and more preferably an aromatic hydrocarbon ring group containing a carbon atom coordinating to MX1, an aromatic heterocyclic group containing a carbon atom coordinating to MX1, or a nitrogen-containing aromatic heterocyclic group containing a nitrogen atom coordinating to MX1.
The bond between MX1 and each of QX11 to QX16 may be a coordination bond or a covalent bond.
In Formula (II), LX11 to LX14 each represent a single or double bond or a connecting group. The connecting group is not particularly limited, but preferably a connecting group containing one or more atoms selected from carbon, nitrogen, oxygen, sulfur, and silicon. Examples of the connecting group are shown below, however, the scope of thereof is not limited by these.
These connecting groups may have a substituent(s), and the substituent may be selected from the examples of the substituents represented by R21 to R24 in Formula (1), and the preferable range thereof is also the same as in Formula (1). LX11 to LX14 are each preferably a single bond, a dimethylmethylene group, or a dimethylsilylene group.
Among compounds represented by Formula (II), compounds represented by the following Formula (X2) are more preferable, and compounds represented by the following Formula (X3) are still more preferable.
The compound represented by Formula (X2) is described first.
In Formula (X2), MX2 represents a metal ion. YX21 to YX26 each represent an atom coordinating to MX2; and QX21 to QX26 each represent an atomic group forming an aromatic ring or an aromatic heterocycle respectively with YX21 to YX26. LX21 to LX24 each represent a single or double bond or a connecting group. The bond between MX2 and each of YX21 to YX26 may be a coordination bond or a covalent bond.
The compound represented by Formula (X2) will be described below in detail.
In Formula (X2), the definition of MX2 is the same as that of MX1 in Formula (II), and their preferable ranges are also the same. YX21 to YX26 each represent an atom coordinating to MX2. The bond between MX2 and each of YX21 to YX26 may be a coordination bond or a covalent bond. Each of YX21 to YX26 is a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and preferably a carbon atom or a nitrogen atom. QX21 to QX26 represent atomic groups forming rings containing YX21 to YX26, respectively, and the rings are each independently selected from aromatic hydrocarbon rings and aromatic heterocycles. The aromatic hydrocarbon rings and aromatic heterocycles may be selected from a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, a thiophene ring, and a furan ring; preferably selected from a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, and a triazole ring; more preferably selected from a benzene ring, a pyridine ring, a pyrazine ring, a pyrazole ring, and a triazole ring; and particularly preferably selected from a benzene ring and a pyridine ring. The aromatic rings may have a condensed ring or a substituent.
The definitions and preferable ranges of LX21 to LX24 are the same as the definitions and preferable ranges of LX11 to LX14 in Formula (II), respectively.
Compounds represented by the following Formula (X3) are more preferable examples of the compounds represented by Formula (II).
The compound represented by Formula (X3) will be described below.
In Formula (X3), MX3 represents a metal ion. YX31 to YX36 each represent a carbon atom, a nitrogen atom, or a phosphorus atom. LX31 to LX34 each represent a single bond, a double bond or a connecting group. The bond between MX3 and each of YX31 to YX36 may be a coordination bond or a covalent bond.
The definition of MX3 is the same as that of MX1 in Formula (II) above, and their preferable ranges are also the same. YX31 to YX36 each represent an atom coordinating to MX3. The bond between MX3 and each of YX31 to YX36 may be a coordination bond or a covalent bond. YX31 to YX36 each represent a carbon atom, a nitrogen atom, or a phosphorus atom, and preferably a carbon atom or a nitrogen atom. The definitions and preferable ranges of LX31 to LX34 are the same as the definitions and preferable ranges of LX11 to LX14 in Formula (II), respectively.
Specific examples of compounds represented by the Formula (I), (II) or (5) include the compounds (1) to (242) described in JP-A No. 2005-310733 and compounds (243) to (245) (their structures being shown below). The invention is not limited thereto.
Among compounds represented by the above-mentioned compound examples, other compounds than compounds having a ligand selected from quadridentate ligands containing bipyridyl or phenanthroline in a partial structure thereof, Schiff base type quadridentate ligands, phenylbipyridyl tridentate ligands, diphenylpyridine tridentate ligands, and terpyridine tridentate ligands, are preferable.
Metal complexes in the invention [compounds represented by Formulae (I), (1), (1-A), (2), (3), (3-A), (3-B), (3-C), (4), (4-A), (5), (5-A), (5-B), (II), (X2), and (X3)] can be synthesized by various techniques.
For example, a metal complex can be obtained by a reaction of a ligand (or its dissociated body) and a metal compound in the presence or absence of a solvent (for example, a halogenated solvent, an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, a nitrile solvent, an amide solvent, a sulfonic solvents, a sulfoxide solvent, or water) in the presence or absence of a base (which may be selected from various inorganic or organic bases, e.g., sodium methoxide, t-butoxy potassium, triethylamine, or potassium carbonate) at room temperature or lower, or under heating (beside the usual heating technique, the technique of heating with a microwave is also effective).
When a metal complex according to the invention is synthesized, the reaction time varies depending on the activity of the reaction raw material, and thus is not particularly limited. The reaction time is preferably from one minute to five days, more preferably from five minutes to three days, and more preferably from ten minutes to one day.
The reaction temperature at synthesis of a metal complex in the invention varies depending on the activity of the reaction, and thus is not particularly limited. The reaction temperature is preferably from 0° C. to 300° C., more preferably from 5° C. to 250° C., and more preferably from 10° C. to 200° C.
Compounds represented by above Formulae (I), (1), (1-A), (2), (3), (3-A), (3-B), (3-C), (4), (4-A), (5), (5-A), (5-B), (II), (X2), and (X3) can be synthesized by appropriately selecting the ligands as partial structures of the desired complex.
For example, the compound represented by the formula (I-A) can be synthesized by adding 6,6′-bis(2-hydroxyphenyl)-2,2′-bipyridyl ligand, its derivative (for example, a 2,9-bis(2-hydroxyphenyl)-1,10-phenanthroline ligand, a 2,9-bis(2-hydroxyphenyl)-4,7-diphenyl-1,10-phenanthroline ligand, or a 6,6′-bis(2-hydroxy-5-tert-butylphenyl)-2,2′-bipyridyl ligand), or the like in an amount of preferably 0.1 to 10 equivalent, more preferably 0.3 to 6 equivalent, and more preferably 0.5 to 4 equivalent relative to the metal compound. In the method for synthesizing the compound represented by the formula (1-A), the reaction solvent, the reaction time, and the reaction temperature are each the same as described above in the method for synthesizing the metal complex according to the invention.
Derivatives of 6,6′-bis(2-hydroxyphenyl)-2,2′-bipyridyl ligand can be synthesized by using various known methods.
For example, a derivative can be synthesized by reacting a 2,2′-bipyridyl derivative (for example, 1,10-phenanthroline) and an anisole derivative (for example, 4-fluoroanisole) by the method described in Journal of Organic Chemistry, 741, 11, (1946). Synthesis can be conducted also by deprotecting a methyl group (by the method described in Journal of Organic Chemistry, 741, 11, (1946), or, for example, by the method of heating in pyridine hydrochloride) after Suzuki coupling reaction using a halogenated 2,2′-bipyridyl derivative (for example, 2,9-dibromo-1,10-phenanthroline) and a 2-methoxy phenylboronate derivative (for example, 2-methoxy-5-fluorophenylboronic acid) or the like as starting materials is carried out. As another alternative, synthesis can be carried out by deprotecting a methyl group (by the method described in Journal of Organic Chemistry, 741, 11, (1946), or, for example, by the method of heating in pyridine hydrochloride) after Suzuki coupling reaction using a 2,2′-bipyridyl boronic acid derivative (for example, 6,6′-bis(4,4,5,5-tetramethyl-1,3,2-dioxabororyl)-2,2′-bipyridyl) and a halogenated anisole derivative (for example, 2-bromo anisole) as starting materials.
In the following, the compounds represented by the following formula (III) will be described.
In Formula (III), Q11 represents an atomic group forming a nitrogen-containing heterocycle; Z11, Z12, and Z13 each represent a substituted or unsubstituted carbon or nitrogen atom; and MY1 represents a metal ion that may further have a ligand.
In Formula (III), Q11 represents an atomic group forming a nitrogen-containing heterocycle that contains the two carbon atoms bonded to Q11 and the nitrogen atom directly bonded to the two carbon atoms. The number of atoms constituting the nitrogen-containing heterocycle formed by Q11 is not particularly limited. The cycle of the nitrogen-containing heterocycle contains preferably from 12 to 20 atoms, more preferably from 14 to 16 atoms, and more preferably 16 atoms.
Z11, Z12, and Z13 each independently represent a substituted or unsubstituted carbon or nitrogen atom. As for the combination of Z11, Z12, and Z13, at least one of Z11, Z12, and Z13 is preferably nitrogen.
Examples of the substituent on the carbon atom include alkyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl), alkenyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as vinyl, allyl, 2-butenyl, and 3-pentenyl), alkynyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl),
aryl groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, and anthranyl), amino groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino), alkoxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, and 2-ethylhexyloxy), aryloxy groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, and 2-naphthyloxy), heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, and quinolyloxy),
acyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, and pivaloyl), alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl), aryloxycarbonyl groups (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), acylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms, such as acetylamino and benzoylamino)
alkoxycarbonylamino groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino groups (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzene sulfonylamino), sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, and particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl),
carbamoyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl), alkylthio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), arylthio groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenylthio), heterocyclic thio groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, and 2-benzothiazolylthio),
sulfonyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group), sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group), ureido groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a ureido group, a methylureido group, and a phenylureido group), phosphoric amide groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include a diethylphosphoric amide group and a phenylphosphoric amide group), a hydroxy group, a mercapto group, halogen atoms (e.g., fluorine, chlorine, bromine, and iodine),
a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, sulfino groups, hydrazino groups, imino groups, heterocyclic groups (preferably having 1 to 30 carbon atoms, and particularly preferably 1 to 12 carbon atoms; the heteroatom(s) may be selected from nitrogen, oxygen and sulfur atoms; examples of the heterocyclic groups include imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, carbazolyl, and azepinyl), silyl groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group), silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy group), and the like. These substituents may themselves have a substituent.
Among these substituents, the substituent on the carbon atom is preferably an alkyl group, an aryl, a heterocyclic group or a halogen atom, more preferably an aryl group or a halogen atom, and still more preferably a phenyl group or a fluorine atom.
The substituent on the nitrogen atom may be selected from the substituents described as examples of the substituent on the carbon atom, and have the same preferable range as in the case of the substituent on the carbon atom.
In Formula (III), MY1 represents a metal ion that may have an additional ligand. MY1 preferably represents a metal ion having no ligand.
The metal ion represented by MY1 is not particularly limited. It is preferably a divalent or trivalent metal ion. The divalent or trivalent metal ion is preferably a cobalt ion, a magnesium ion, a zinc ion, a palladium ion, a nickel ion, a copper ion, a platinum ion, a lead ion, an aluminum ion, an iridium ion, or a europium ion, more preferably a cobalt ion, a magnesium ion, a zinc ion, a palladium ion, a nickel ion, a copper ion, a platinum ion, or a lead ion, still more preferably a copper ion or a platinum ion, and particularly preferably a platinum ion. MY1 may or may not be bound to an atom contained in Q11, and is preferably bound to an atom contained in Q11.
The additional ligand that MY1 may have is not particularly limited, but is preferably a monodentate or bidentate ligand, and more preferably a bidentate ligand. The coordinating atom is not particularly limited, but preferably an oxygen atom, a sulfur atom, a nitrogen atom, a carbon atom, or a phosphorus atom, more preferably an oxygen atom, a nitrogen atom, or a carbon atom, and still more preferably an oxygen atom or a nitrogen atom.
Preferable examples of compounds represented by Formula (III) include compounds represented by the following Formulae (a) to (j) and the tautomers thereof.
Compounds represented by Formula (III) are more preferably selected from compounds represented by Formula (a) or (b) and tautomers thereof, and still more preferably selected from compounds represented by Formula (b).
Compounds represented by Formula (c) or (g) are also preferable as the compounds represented by Formula (III).
A compound represented by Formula (c) is preferably a compound represented by Formula (d), a tautomer of a compound represented by Formula (d), a compound represented by Formula (e), a tautomer of a compound represented by Formula (e), a compound represented by Formula (f) or a tautomer of a compound represented by Formula (f); more preferably a compound represented by Formula (d), a tautomer of a compound represented by Formula (d), a compound represented by Formula (e), or a tautomer of a compound represented by Formula (e); and still more preferably a compound represented by Formula (d) or a tautomer of a compound represented by Formula (d).
A compound represented by Formula (g) is preferably a compound represented by Formula (h), a tautomer of a compound represented by Formula (h), a compound represented by Formula (i), a tautomer of a compound represented by Formula (i), a compounds represented by Formula (j) or a tautomer of a compounds represented by Formula (j); more preferably a compound represented by Formula (h), a tautomers of a compound represented by Formula (h), a compound represented by Formula (i), or a tautomer of a compound represented by Formula (i); and still more preferably a compound represented by Formula (h) or a tautomer of a compound represented by Formula (h).
Hereinafter, the compounds represented by Formulae (a) to (j) will be described in detail.
The compound represented by Formula (a) will be described below.
In Formula (a), the definitions and preferable ranges of Z21, Z22, Z23, Z24, Z25, Z26, and M21 are the same as the definitions and preferable ranges of corresponding Z11, Z12, Z13, Z11, Z12, Z13, and MY1 in Formula (III), respectively.
Q21 and Q22 each represent a group forming a nitrogen-containing heterocycle. Each of the nitrogen-containing heterocycles formed by Q21 and Q22 is not particularly limited, but is preferably a pyrrole ring, an imidazole ring, a triazole ring, a condensed ring containing one or more of the above rings (e.g., benzopyrrole), or a tautomer of any of the above rings (e.g., in Formula (b) below, the nitrogen-containing five-membered ring substituted by R43 and R44, or by R45 and R46 is defined as a tautomer of pyrrole), and more preferably a pyrrole ring or a condensed ring containing a pyrrole ring (e.g., benzopyrrole).
X21, X22, X23, and X24 each independently represent a substituted or unsubstituted carbon or nitrogen atom, preferably an unsubstituted carbon or nitrogen atom, and more preferably a nitrogen atom.
The compound represented by Formula (b) will be described below.
In Formula (b), the definitions and preferable ranges of Z41, Z42, Z43, Z44, Z45, Z46, X41, X42, X43, X44, and M41 are the same as the definitions and preferable ranges of Z21, Z22, Z23, Z24, Z25, Z26, X21, X22, X23, X24, and M21 in Formula (a), respectively.
R43, R44, R45, and R46 are each preferably selected from a hydrogen atom or a substituent. The substituent may be selected from the above-described examples of the substituent on the carbon atom represented by Z11 or Z12 in Formula (III)
R43, R44, R45, and R46 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the groups described above as examples of the substituent on the carbon atom represented by Z11 or Z12 in Formula (III).
The compound represented by Formula (c) will be described below.
In Formula (c), Z101, Z102, and Z103 each independently represent a substituted or unsubstituted carbon or nitrogen atom. At least one of Z101, Z102, and Z103 is preferably a nitrogen atom.
L101, L102, L103, and L104 each independently represent a single bond or a connecting group. The connecting group is not particularly limited, and examples thereof include a carbonyl connecting group, an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, a nitrogen-containing heterocycle connecting group, a connecting group which connects moieties via an oxygen atom, an amino connecting group, an imino connecting group, a carbonyl connecting group, and connecting groups comprising combinations thereof.
L101, L102, L103, and L104 are each preferably a single bond, an alkylene group, an alkenylene group, an amino connecting group, or an imino connecting group, more preferably a single bond, an alkylene connecting group, an alkenylene connecting group, or an imino connecting group, and still more preferably a single bond or an alkylene connecting group.
Q101 and Q103 each independently represent a group containing a carbon atom coordinating to M101, a group containing a nitrogen atom coordinating to M101, a group containing a phosphorus atom coordinating to M101, a group containing an oxygen atom coordinating to M101, or a group containing a sulfur atom coordinating to M101.
The group containing a carbon atom coordinating to M101 is preferably an aryl group containing a coordinating carbon atom, a five-membered ring heteroaryl group containing a coordinating carbon atom, or a six-membered ring heteroaryl group containing a coordinating carbon atom; more preferably, an aryl group containing a coordinating carbon atom, a nitrogen-containing five-membered ring heteroaryl group containing a coordinating carbon atom, or a nitrogen-containing six-membered ring heteroaryl group containing a coordinating carbon atom; and still more preferably, an aryl group containing a coordinating carbon atom.
The group containing a nitrogen atom coordinating to M101 is preferably a nitrogen-containing five-membered ring heteroaryl group containing a coordinating nitrogen atom or a nitrogen-containing six-membered ring heteroaryl group containing a coordinating nitrogen atom, and more preferably a nitrogen-containing six-membered ring heteroaryl group containing a coordinating nitrogen atom.
The group containing a phosphorus atom coordinating to M101 is preferably an alkyl phosphine group containing a coordinating phosphorus atom, an aryl phosphine group containing a coordinating phosphorus atom, an alkoxyphosphine group containing a coordinating phosphorus atom, an aryloxyphosphine group containing a coordinating phosphorus atom, a heteroaryloxyphosphine group containing a coordinating phosphorus atom, a phosphinine group containing a coordinating phosphorus atom, or a phosphor group containing a coordinating phosphorus atom; more preferably, an alkyl phosphine group containing a coordinating phosphorus atom or an aryl phosphine group containing a coordinating phosphorus atom.
The group containing an oxygen atom coordinating to M101 is preferably an oxy group or a carbonyl group containing a coordinating oxygen atom, and more preferably an oxy group.
The group containing a sulfur atom coordinating to M101 is preferably a sulfide group, a thiophene group, or a thiazole group, and more preferably a thiophene group.
Each of Q101 and Q103 is preferably a group containing a carbon atom coordinating to M101, a group containing a nitrogen atom coordinating to M101, or a group containing a an oxygen atom coordinating to M101; more preferably a group containing a carbon atom coordinating to M101 or a group containing a nitrogen atom coordinating to M101; and still more preferably a group containing a carbon atom coordinating to M101.
Q102 represents a group containing a nitrogen atom coordinating to M101, a group containing a phosphorus atom coordinating to M101, a group containing an oxygen atom coordinating to M101 or a group containing a sulfur atom coordinating to M101, and preferably a group containing a nitrogen atom coordinating to M101.
The definition of M101 is the same as that of M11 in Formula (I), and their preferable ranges are also the same.
The compound represented by Formula (d) will be described below.
In Formula (d), the definitions and preferable ranges Z201, Z202, Z203, Z207, Z208, Z209, L201, L202, L203, L204, and M201 are the same as the definitions and preferable ranges Z101, Z102, Z103, Z101, Z102, Z103, L101, L102, L103, L104, and M101 in Formula (c), respectively. Z204, Z205, Z206, Z210, Z211, and Z212 each represent a substituted or unsubstituted carbon or a substituted or unsubstituted nitrogen atom, and preferably a substituted or unsubstituted carbon atom.
The compound represented by Formula (e) will be described below.
In Formula (e), the definitions and preferable ranges of Z301, Z302, Z303, Z304, Z305, Z306, Z307, Z308, Z309, Z310, L301, L302, L303, L304, and M301 are the same as the definitions and preferable ranges of corresponding Z201, Z202, Z203, Z204, Z206, Z207, Z208, Z209, Z210, Z212, L101, L102, L103, L104, and M101 in formulae (d) and (c), respectively.
The compound represented by Formula (f) will be described below.
In Formula (f), the definitions and preferable ranges of Z401, Z402, Z403, Z404, Z405, Z406, Z407, Z408, Z409, Z410, Z411, Z412, L401, L402, L403, L404, and M401 are the same as the definitions and preferable ranges of corresponding Z201, Z202, Z203, Z204, Z205, Z206, Z207, Z208, Z209, Z210, Z211, Z212, L101, L102, L103, L104, and M101 in formulae (d) and (c), respectively. X401 and X402 each represent an oxygen atom or a substituted or unsubstituted nitrogen or a sulfur atom, preferably an oxygen atom or a substituted nitrogen atom, and more preferably an oxygen atom.
The compound represented by Formula (g) will be described below.
In Formula (g), the definitions and preferable ranges of Z501, Z502, Z503, L501, L502, L503, L504, Q501, Q502, Q503, and M501 are the same as the definitions and preferable ranges of corresponding Z101, Z102, Z103, L101, L102, L103, L104, Q101, Q103, Q102, and M101 in Formula (c), respectively.
The compound represented by Formula (h) will be described below.
In Formula (h), the definitions and preferable ranges of Z601, Z602, Z603, Z604, Z605, Z606, Z607, Z608, Z609, Z610, Z611, Z612, L601, L602, L603, L604, and M601 are the same as the definitions and preferable ranges of corresponding Z201, Z202, Z203, Z207, Z208, Z209, Z204, Z205, Z206, Z210, Z211, Z212, L101, L102, L103, L104, and M101 in Formulae (d) and (c), respectively.
The compound represented by Formula (i) will be described below.
In Formula (i), the definitions and preferable ranges of Z701, Z702, Z703, Z704, Z705, Z706, Z707, Z708, Z709, Z710, L701, L702, L703, L704, and M701 are the same as the definitions and preferable ranges of corresponding Z201, Z202, Z203, Z207, Z208, Z209, Z204, Z206, Z210, Z212, L101, L102, L103, L104, and M101 in Formulae (d) and (c), respectively.
The compound represented by Formula (j) will be described below.
In Formula (j), the definitions and preferable ranges of Z801, Z802, Z803, Z804, Z805, Z806, Z807, Z808, Z809, Z810, Z811, Z812, L801, L802, L803, L804, M801, X801, and X802 are the same as the definitions and preferable ranges of corresponding Z201, Z202, Z203, Z207, Z208, Z209, Z204, Z205, Z206, Z210, Z211, Z212, L101, L102, L103, L104, M101, X401 and X402 in Formulae (d), (c), and (f), respectively.
Specific examples of compounds represented by Formula (III) include compounds (2) to (8), compounds (15) to (20), compound (27) to (32), compounds (36) to (38), compounds (42) to (44), compounds (50) to (52), and compounds (57) to (154) described in Japanese Patent Application No. 2004-88575, the disclosure of which is incorporated herein by reference. The structures of the above compounds are shown below, however, the scope of the invention is not limited thereto.
Preferable examples of the metal complex usable in the invention further include compounds represented by Formula (A-1), (B-1), (C-1), (D-1), (E-1), or (F-1) described below.
Formula (A-1) is described below.
In Formula (A-1), MA1 represents a metal ion. YA11, YA14, YA15 and YA18 each independently represent a carbon atom or a nitrogen atom. YA12, YA13, YA16 and YA17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LA11, LA12, LA13 and LA14 each represent a connecting group, and may have the same structure as each other or different structure from each other. QA11 and QA12 each independently represent a partial structure containing an atom bonded to MA1.
The compound represented by Formula (A-1) will be described in detail.
MA1 represents a metal ion. The metal ion is not particularly limited. It is preferably a divalent metal ion, more preferably Pt2+, Pd2+, Cu2+, Ni2+, Co2+, Zn2+, Mg2+ or Pb2+, still more preferably Pt2+ or Cu2+, and further more preferably Pt2+.
YA11, YA14, YA15 and YA18 each independently represent a carbon atom or a nitrogen atom. Each of YA11, YA14, YA15 and YA18 is preferably a carbon atom.
YA12, YA13, YA16 and YA17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. Each of YA12, YA13, YA16 and YA17 is preferably a substituted or unsubstituted carbon atom or a substituted or unsubstituted nitrogen atom.
LA11, LA12, LA13 and LA14 each independently represent a divalent connecting group. The divalent connecting group represented by LA11, LA12, LA13 or LA14 may be, for example, a single bond or a connecting group formed of atoms selected from carbon, nitrogen, silicon, sulfur, oxygen, germanium, phosphorus and the like, more preferably a single bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, a substituted silicon atom, an oxygen atom, a sulfur atom, a divalent aromatic hydrocarbon cyclic group or a divalent aromatic heterocyclic group, still more preferably a single bond, a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, a substituted silicon atom, a divalent aromatic hydrocarbon cyclic group or a divalent aromatic heterocyclic group, and further more preferably a single bond or a substituted or unsubstituted methylene group. Examples of the divalent connecting group represented by LA11, LA12, LA13 or LA14 include the following groups:
The divalent connecting group represented by LA11, LA12, LA13 or LA14 may further have a substituent. The substituent which can be introduced into the divalent connecting group may be, for example, an alkyl group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group), an alkenyl group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), an alkynyl group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 10 carbon atoms, and examples thereof include a propargyl group and a 3-pentynyl group),
an aryl group (preferably those having 6 to 30 carbon atoms, more preferably those having 6 to 20 carbon atoms, particularly preferably those having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a p-methylphenyl group, a naphthyl group, and an anthranyl group), an amino group preferably those having 0 to 30 carbon atoms, more preferably those having 0 to 20 carbon atoms, particularly preferably those having 0 to 10 carbon atoms, and examples thereof include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, and a ditolylamino group), an alkoxy group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a butoxy group, and a 2-ethylhexyloxy group), an aryloxy group (preferably those having 6 to 30 carbon atoms, more preferably those having 6 to 20 carbon atoms, particularly preferably those having 6 to 12 carbon atoms, and examples thereof include a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group),
a heterocyclic oxy group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, and a quinolyloxy group), an acyl group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), an alkoxycarbonyl group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 12 carbon atoms, and examples thereof include a methoxycarbonyl group, and an ethoxycarbonyl group), an aryloxycarbonyl group (preferably those having 7 to 30 carbon atoms, more preferably those having 7 to 20 carbon atoms, particularly preferably those having 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonyl group),
an acyloxy group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 10 carbon atoms, and examples thereof include an acetoxy group, and a benzoyloxy group), an acylamino group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 10 carbon atoms, and examples thereof include an acetylamino group, and a benzoylamino group), an alkoxycarbonylamino group (preferably those having 2 to 30 carbon atoms, more preferably those having 2 to 20 carbon atoms, particularly preferably those having 2 to 12 carbon atoms, and examples thereof include a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably those having 7 to 30 carbon atoms, more preferably those having 7 to 20 carbon atoms, particularly preferably those having 7 to 12 carbon atoms, and examples thereof include a phenyloxycarbonylamino group),
a sulfonylamino group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a methanesulfonylamino group and a benzenesulfonylamino group), a sulfamoyl group (preferably those having 0 to 30 carbon atoms, more preferably those having 0 to 20 carbon atoms, particularly preferably those having 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group), a carbamoyl group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group),
an alkylthio group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a methylthio group and an ethylthio group), an arylthio group (preferably those having 6 to 30 carbon atoms, more preferably those having 6 to 20 carbon atoms, particularly preferably those having 6 to 12 carbon atoms, and examples thereof include a phenylthio group), a heterocyclic thio group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a pyridylthio group, a 2-benzimidazolylthio group, a 2-benzoxazolylthio group, and a 2-benzthiazolylthio group), a sulfonyl group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group), a sulfinyl group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a methanesulfinyl group and a benzenesulfinyl group),
a ureido group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a ureido group, a methylureido group, and a phenylureido group), a phosphoric amide group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, particularly preferably those having 1 to 12 carbon atoms, and examples thereof include a diethylphosphoric amide group and a phenylphosphoric amide group), a hydroxy group, a mercapto group, a halogen atom (and examples thereof include a fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group,
a heterocyclic group (preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 12 carbon atoms, containing a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom; specific examples thereof include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, a carbazolyl group, and an azepinyl group), a silyl group (preferably those having 3 to 40 carbon atoms, more preferably those having 3 to 30 carbon atoms, particularly preferably those having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group) or a silyloxy group (preferably those having 3 to 40 carbon atoms, more preferably those having 3 to 30 carbon atoms, particularly preferably those having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy group).
These substituents may themselves have a substituent. The substituent which can be introduced to these substituents is preferably selected from an alkyl group, an aryl group, a heterocyclic group, a halogen atom and a silyl group, more preferably selected from an alkyl group, an aryl group, a heterocyclic group and a halogen atom, and still more preferably selected from an alkyl group, an aryl group, an aromatic heterocyclic group and a fluorine atom.
QA11 and QA12 each independently represent a partial structure containing an atom covalently bonded to MA1. QA11 and QA12 each independently preferably represent a group having a carbon atom bonded to MA1, a group having a nitrogen atom bonded to MA1, a group having a silicon atom bonded to MA1, a group having a phosphorus atom bonded to MA1, a group having an oxygen atom bonded to MA1 or a group having a sulfur atom bonded to MA1, more preferably a group having a carbon, nitrogen, oxygen, or sulfur atom bonded to MA1, still more preferably a group having a carbon or nitrogen atom bonded to MA1, and further more preferably a group having a carbon atom bonded to MA1.
The group bonded to MA1 via a carbon atom is preferably an aryl group having a carbon atom bonded to MA1, a 5-membered cyclic heteroaryl group having a carbon atom bonded to MA1 or a 6-membered cyclic heteroaryl group having a carbon atom bonded to MA1, more preferably an aryl group having a carbon atom bonded to MA1, a nitrogen-containing 5-membered cyclic heteroaryl group having a carbon atom bonded to MA1 or a nitrogen-containing 6-membered cyclic heteroaryl group having a carbon atom bonded to MA1, and still more preferably an aryl group having a carbon atom bonded to MA1.
The group bonded to MA1 via a nitrogen atom is preferably a substituted amino group or a nitrogen-containing 5-membered cyclic heteroaryl group having a nitrogen atom bonded to MA1, more preferably a nitrogen-containing 5-membered cyclic heteroaryl group having a nitrogen atom bonded to MA1.
The group bonded to MA1 via a phosphorus atom is preferably a substituted phosphino group. The group having a silicon atom bonded to MA1 is preferably a substituted silyl group. The group having an oxygen atom bonded to MA1 is preferably an oxy group, and the group having a sulfur atom bonded to MA1 is preferably a sulfide group.
The compound represented by Formula (A-1) is more preferably a compound represented by the following Formula (A-2), (A-3) or (A-4).
In Formula (A-2), MA2 represents a metal ion YA21, YA24, YA25 and YA28 each independently represent a carbon atom or a nitrogen atom. YA22, YA23, YA26 and YA27 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LA21, LA22, LA23 and LA24 each independently represent a connecting group. ZA21, ZA22, ZA24, ZA25 and ZA26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (A-3), MA3 represents a metal ion. YA31, YA34, YA35 and YA38 each independently represent a carbon atom or a nitrogen atom. YA32, YA33, YA36 and YA37 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LA31, LA32, LA33 and LA34 each independently represent a connecting group. ZA31, ZA32 ZA33 and ZA34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (A-4), MA4 represents a metal ion YA41, YA44, YA45 and YA48 each independently represent a carbon atom or a nitrogen atom. YA42, YA43, YA46 and YA47 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LA41, LA42, LA43 and LA44 each independently represent a connecting group. ZA41, ZA42, ZA43, ZA44, ZA45 and ZA46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. XA41 and XA42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom.
The compound represented by Formula (A-2) will be described in detail.
MA2, YA21, YA24, YA25, YA28, YA22, YA23, YA26, YA27, LA21, LA22, LA23 and LA24 have the same definitions as corresponding MA1, YA11, YA14, YA15, YA18, YA12, YA13, YA16, YA17, LA11, LA12, LA13 and LA14 in Formula (A-1) respectively, and their preferable examples are also the same.
ZA21, ZA22, ZA23, ZA24, ZA25 and ZA26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. ZA21, ZA22, ZA23, ZA24, ZA25 and ZA26 each independently represent preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1)
The compound represented by Formula (A-3) will be described in detail.
MA3, YA31, YA34, YA35, YA38, YA32, YA33, YA36, YA37, LA31, LA32, LA33 and LA34 have the same definitions as corresponding MA1, YA11, YA14, YA15, YA18, YA12, YA13, YA16, YA17, LA11, LA12, LA13 and LA14 in Formula (A-1) respectively, and their preferable examples are also the same.
ZA31, ZA32, ZA33 and ZA34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZA31, ZA32, ZA33 and ZA34 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1).
The compound represented by Formula (A-4) will be described in detail.
MA4, YA41, YA44, YA45, YA48, YA42, YA43, YA46, YA47, LA41, LA42, LA43 and LA44 have the same definitions as corresponding MA1, YA11, YA14, YA15, YA18, YA12, YA13, YA16, YA17, LA11, LA12, LA13 and LA14 in Formula (A-1) respectively, and their preferable examples are also the same.
ZA41, ZA42, ZA43, ZA44, ZA45 and ZA46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZA41, ZA42, ZA43, ZA44, ZA45 and ZA46 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1).
XA41 and XA42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom. Each of XA41 and XA42 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
Specific examples of the compound represented by Formula (A-1) are shown below. However, the specific examples should not be construed as limiting the invention.
Compounds represented by Formula (B-1) shown below are also preferable as metal complexes usable in the invention.
In Formula (B-1), MB1 represents a metal ion. YB11, YB14, YB15 and YB18 each on atom or a nitrogen atom. YB12, YB13, YB16 and YB17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LB11, LB12, LB13 and LB14 each independently represent a connecting group. QB11 and QB12 each independently represent a partial structure containing an atom bonded to MB1.
The compound represented by Formula (B-1) will be described in detail.
In Formula (B-1), MB1, YB11, YB14, YB15, YB18 YB12, YB13, YB16, YB17, LB11, LB12, LB13, LB14, QB11 and QB12 have the same definitions as corresponding MA1, YA11, YA14, YA15, YA18 YA12, YA13, YA16, YA17, LA11, LA12, LA13, LA14, QA11 and QA12 in Formula (A-1) respectively, and their preferable examples are also the same.
More preferable examples of the compound represented by Formula (B-1) include compounds represented by the following Formula (B-2), (B-3) or (B-4).
In Formula (B-2), MB2 represents a metal ion. YB21, YB24, YB25 and YB28 each independently represent a carbon atom or a nitrogen atom. YB22, YB23, YB26 and YB27 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LB21, LB22, LB23 and LB24 each independently represent a connecting group. ZB21, ZB22, ZB23, ZB24, ZB25 and ZB26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (B-3), MB3 represents a metal ion. YB31, YB34, YB35 and YB38 each independently represent a carbon atom or a nitrogen atom. YB32, YB33, YB36 and YB37 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LB31, LB32, LB33 and LB34 each independently represent a connecting group. ZB31, ZB32, ZB33 and ZB34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (B-4), MB4 represents a metal ion. YB41, YB44, YB45 and YB48 each independently represent a carbon atom or a nitrogen atom. YB42, YB43, YB46 and YB47 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom. LB41, LB42, LB43 and LB44 each independently represent a connecting group. ZB41, ZB42, ZB43, ZB44, ZB45 and ZB46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. XB41 and XB42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom.
The compound represented by Formula (B-2) will be described in detail.
In Formula (B-2), MB2, YB21, YB24, YB25, YB28, YB22, YB23, YB26, YB27, LB21, LB22, LB23 and LB24 have the same definitions as corresponding MB1, YB11, YB14, YB15, YB18, YB12, YB13, YB16, YB17, LB11, LB12, LB13 and LB14 in Formula (B-1) respectively, and their preferable examples are also the same.
ZB21, ZB22, ZB23, ZB24, ZB25 and ZB26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZB21, ZB22, ZB23, ZB24, ZB25 and ZB26 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1).
The compound represented by Formula (B-3) will be described in detail.
In Formula (B-3), MB3, YB31, YB34, YB35, YB38, YB32, YB33, YB36, YB37, LB31, LB32, LB33 and LB34 have the same definitions as corresponding MB1, YB11, YB14, YB15, YB18, YB12, YB13, YB16, YB17, LB11, LB12, LB13 and LB14 in Formula (B-1) respectively, and their preferable examples are also the same.
ZB31, ZB32, ZB33 and ZB34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZB31, ZB32, ZB33 and ZB34 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1)
The compound represented by Formula (B-4) will be described in detail.
In Formula (B-4), MB4, YB41, YB44, YB45, YB48, YB42, YB43, YB46, YB47, LB41, LB42, LB43 and LB44 have the same definitions as corresponding MB1, YB11, YB14, YB15, YB18, YB12, YB13, YB16, YB17, LB11, LB12, LB13 and LB14 in Formula (B-1) respectively, and their preferable examples are also the same.
ZB41, ZB42, ZB43, ZB44, ZB45 and ZB46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZB41, ZB42, ZB43, ZB44, ZB45 and ZB46 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1).
XB41 and XB42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom. Each of XB41 and XB42 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
Specific examples of the compounds represented by Formula (B-1) are illustrated below, but the invention is not limited thereto.
An example of preferable metal complexes usable in the invention is a compound represented by the following Formula (C-1).
In Formula (C-1), MC1 represents a metal ion. RC11 and RC12 each independently represent a hydrogen atom or a substituent. When RC11 and RC12 represent substituents, the substituents may be bonded to each other to form a 5-membered ring. RC13 and RC14 each independently represent a hydrogen atom or a substituent. When RC13 and RC14 represent substituents, the substituents may be bonded to each other to form a 5-membered ring. GC11 and GC12 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. LC11 and LC12 each independently represent a connecting group. QC11 and QC12 each independently represent a partial structure containing an atom covalently bonded to MC1.
Formula (C-1) will be described in detail.
In Formula (C-1), MC1, LC11, LC12, QC11 and QC12 have the same definitions as corresponding MA1, LA1, LA12, QA11 and QA12 in Formula (A-1) respectively, and their preferable examples are also the same.
GC11 and GC12 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom, preferably a nitrogen atom or an unsubstituted carbon atom, and more preferably a nitrogen atom.
RC11 and RC12 each independently represent a hydrogen atom or a substituent. RC11 and RC12 may be bonded to each other to form a 5-membered ring. RC13 and RC14 each independently represent a hydrogen atom or a substituent. RC13 and RC14 may be bonded to each other to form a 5-membered ring.
The substituent represented by RC11, RC12, RC13 or RC14 may be, for example, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 10 carbon atoms; and examples thereof include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms; and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms; and examples thereof include a propargyl group and a 3-pentynyl group),
an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms; and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), an amino group (preferably having 0 to 30 carbon atoms, more preferably having 0 to 20 carbon atoms, particularly preferably having 0 to 10 carbon atoms; and examples thereof include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, and a ditolylamino group), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 10 carbon atoms; and examples thereof include a methoxy group, an ethoxy group, a butoxy group, and a 2-ethylhexyloxy group), an aryloxy group (preferably a having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms; and examples thereof include a phenyloxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group),
a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms; and examples thereof include a pyridyloxy group, a pyrazyloxy group, a pyrimidyloxy group, and a quinolyloxy group), an acyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms; and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), an alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms; and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms; and examples thereof include a phenyloxycarbonyl group),
an acyloxy group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms; and examples thereof include an acetoxy group and a benzoyloxy group), an acylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms; and examples thereof include an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms; and examples thereof include a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms; and examples thereof include a phenyloxycarbonylamino group),
an alkylthio group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms; and examples thereof include a methylthio group and an ethylthio group), an arylthio group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms; and examples thereof include a phenylthio group), a heterocyclic thio group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms; and examples thereof include a pyridylthio group, a 2-benzimidazolylthio group, a 2-benzoxazolylthio group, and a 2-benzthiazolylthio group), a halogen atom (such as a fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group,
a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and containing a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom; examples include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a, piperidyl group, a morpholino group, a benzoxazolyl group, a benzimidazolyl group, a benzthiazolyl group, a carbazolyl group, and an azepinyl group), a silyl group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably having 3 to 24 carbon atoms; and examples thereof include a trimethylsilyl group, and a triphenylsilyl group) or a silyloxy group (preferably having 3 to 40 carbon atoms, more preferably having 3 to 30 carbon atoms, particularly preferably having 3 to 24 carbon atoms; and examples thereof include a trimethylsilyloxy group and a triphenylsilyloxy group).
The substituent represented by RC11, RC12, RC13 or RC14 is preferably an alkyl group, an aryl group, or such a group that RC11 and RC12, or RC13 and RC14, are bonded to each other to form a 5-membered ring. In a particularly preferable embodiment, RC11 and RC12, or RC13 and RC14, are bonded to each other to form a 5-membered ring.
The compound represented by Formula (C-1) is more preferably a compound represented by Formula (C-2).
In Formula (C-2), MC2 represents a metal ion.
YC21, YC22, YC23 and YC24 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. GC21 and GC22 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. LC21 and LC22 each independently represent a connecting group. QC21 and QC22 each independently represent a partial structure containing an atom bonded to MC2.
Formula (C-2) will be described in detail.
In Formula (C-2), MC2, LC21, LC22, QC21, QC22, GC21 and GC22 have the same definitions as corresponding MC1, LC11, LC12, QC11, QC12, GC11 and GC12 in Formula (C-1) respectively, and their preferable examples are also the same.
YC21, YC22, YC23 and YC24 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom, preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.
The compound represented by Formula (C-2) is more preferably a compound represented by the following Formula (C-3), (C-4) or (C-5).
In Formula (C-3), MC3 represents a metal ion.
YC31, YC32, YC33 and YC34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. GC31 and GC32 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. LC31 and LC32 each independently represent a connecting group. ZC31, ZC32, ZC33, ZC34, ZC35 and ZC36 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (C-4), MC4 represents a metal ion.
YC41, YC42, YC43 and YC44 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. GC41 and GC42 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. LC41 and LC42 each independently represent a connecting group. ZC41, ZC42, ZC43 and ZC44 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (C-5), MC5 represents a metal ion.
YC51, YC52, YC53 and YC54 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. GC51 and GC52 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. LC51 and LC52 each independently represent a connecting group. ZC51, ZC52, ZC53, ZC54, ZC55 and ZC56 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. XC51 and XC52 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom.
The compound represented by Formula (C-3) will be described in detail.
In Formula (C-3), MC3, LC31, LC32, GC31 and GC32 have the same definitions as corresponding MC1, LC11, LC12, GC11 and GC12 in Formula (C-1) respectively, and their preferable examples are also the same.
ZC31, ZC32, ZC33, ZC34, ZC35 and ZC36 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZC31, ZC32, ZC33, ZC34, ZC35 and ZC36 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.
The compound represented by Formula (C-4) is described in more detail.
In Formula (C-4), MC4, LC41, LC42, GC41 and GC42 have the same definitions as corresponding MC1, LC11, LC12, GC11 and GC12 in Formula (C-1) respectively, and their preferable examples are also the same.
ZC41, ZC42, ZC43, and ZC44 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZC41, ZC42, ZC43 and ZC44 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.
The compound represented by Formula (C-5) is described in more detail.
MC5, LC51, LC52, GC51 and GC52 have the same definitions as corresponding MC1, LC11, LC12, GC11 and GC12 in Formula (C-1) respectively, and their preferable examples are also the same.
ZC51, ZC52, ZC53, ZC54, ZC55 and ZC56 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZC51, ZC52, ZC53, ZC54, ZC55 and ZC56 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.
XC51 and XC52 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom. Each of XC51 and XC52 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
Specific examples of the compounds represented by Formula (C-1) are illustrated below, however, the invention is not limited thereto.
An example of preferable metal complexes usable in the invention is a compound represented by the following Formula (D-1).
In Formula (D-1), MD1 represents a metal ion.
GD11 and GD12 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. JD11, JD12, JD13 and JD14 each independently represent an atomic group necessary for forming a 5-membered ring. LD11 and LD12 each independently represent a connecting group.
Formula (D-1) will be described in detail.
In Formula (D-1), MD1, LD11 and LD12 have the same definitions as corresponding MA1, LA11 and LA12 in Formula (A-1) respectively, and their preferable examples are also the same.
GD11 and GD12 have the same definitions as corresponding GC11 and GC12 in Formula (C-1) respectively, and their preferable examples are also the same.
JD11, JD12, JD13 and JD14 each independently represent an atomic group necessary for forming a nitrogen-containing 5-membered heterocycle containing the atomic group.
The compound represented by Formula (D-1) is more preferably a compound represented by the following Formula (D-2), (D-3) or (D-4).
In Formula (D-2), MD2 represents a metal ion.
GD21 and GD22 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
YD21, YD22, YD23 and YD24 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
XD21, XD22, XD23 and XD24 each independently represent an oxygen atom, a sulfur atom, —NRD21— or —C(RD22)RD23—.
RD21, RD22 and RD23 each independently represent a hydrogen atom or a substituent. LD21 and LD22 each independently represent a connecting group.
In Formula (D-3), MD3 represents a metal ion.
GD31 and GD32 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
YD31, YD32, YD33 and YD34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
XD31, XD32, XD33 and XD34 each independently represent an oxygen atom, a sulfur atom, —NRD31— or —C(RD32)RD33—.
RD31, RD32 and RD33 each independently represent a hydrogen atom or a substituent. LD31 and LD32 each independently represent a connecting group.
In Formula (D-4), MD4 represents a metal ion.
GD41 and GD42 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
YD41, YD42, YD43 and YD44 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
XD41, XD42, XD43 and XD44 each independently represent an oxygen atom, a sulfur atom, —NRD41— or —C(RD42)RD43—. RD41, RD42 and RD43 each independently represent a hydrogen atom or a substituent. LD41 and LD42 each independently represent a connecting group.
Formula (D-2) will be described in detail.
In Formula (D-2), MD2, LD21, LD22, GD21 and GD22 have the same definitions as corresponding MD1, LD11, LD12, GD11 and GD12 in Formula (D-1) respectively, and their preferable examples are also the same.
YD21, YD22, YD23 and YD24 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom, preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom.
XD21, XD22, XD23 and XD24 each independently represent an oxygen atom, a sulfur atom, —NRD21— or —C(RD22)RD23—, preferably a sulfur atom, —NRD21— or —C(RD22)RD23—, more preferably —NRD21— or —C(RD22)RD23—, and further more preferably —NRD21—.
RD21, RD22 and RD23 each independently represent a hydrogen atom or a substituent. The substituent represented by RD21, RD22 or RD23 may be, for example, an alkyl group (preferably those having 1 to 20 carbon atoms, more preferably those having 1 to 12 carbon atoms, particularly preferably those having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, an iso-propyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group), an alkenyl group (preferably those having 2 to 20 carbon atoms, more preferably those having 2 to 12 carbon atoms, particularly preferably those having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), an alkynyl group (preferably those having 2 to 20 carbon atoms, more preferably those having 2 to 12 carbon atoms, particularly preferably those having 2 to 8 carbon atoms, and examples thereof include a propargyl group and a 3-pentynyl group),
an aryl group (preferably those having 6 to 30 carbon atoms, more preferably those having 6 to 20 carbon atoms, particularly preferably those having 6 to 12 carbon atoms group, and examples thereof include a phenyl group, a p-methylphenyl group, and a naphthyl group), a substituted carbonyl group (preferably those having 1 to 20 carbon atoms, more preferably those having 1 to 16 carbon atoms, particularly preferably those having 1 to 12 carbon atoms group, and examples thereof include a acetyl group, a benzoyl group, a methoxycarbonyl group, a phenyloxycarbonyl group, a dimethylaminocarbonyl group, and a phenylaminocarbonyl group), a substituted sulfonyl group (preferably those having 1 to 20 carbon atoms, more preferably those having 1 to 16 carbon atoms, particularly preferably those having 1 to 12 carbon atoms group, and examples thereof include a mesyl group and a tosyl group), or
a heterocyclic group (including an aliphatic heterocyclic group and aromatic heterocyclic group, preferably those having 1 to 50 carbon atoms, more preferably those having 1 to 30 carbon atoms, more preferably those having 2 to 12 carbon atoms, preferably containing an oxygen atom, a sulfur atom or a nitrogen atom, and examples thereof include an imidazolyl group, a pyridyl group, a furyl group, a piperidyl group, a morpholino group, a benzoxazolyl group, and a triazolyl group). Each of RD21, RD22 and RD23 is preferably an alkyl group, aryl group or aromatic heterocyclic group, more preferably an alkyl or aryl group, and still more preferably an aryl group.
Formula (D-3) will be described in detail.
In Formula (D-3), MD3, LD31, LD32, GD31 and GD32 have the same definitions as corresponding MD1, LD11, LD12, GD11 and GD12 in Formula (D-1) respectively, and their preferable examples are also the same.
XD31, XD32, XD33 and XD34 have the same definitions as corresponding XD21, XD22, XD23 and XD24 in Formula (D-2) respectively, and their preferable examples are also the same.
YD31, YD32, YD33 and YD34 have the same definitions as corresponding YD21, YD22, YD23 and YD24 in Formula (D-2) respectively, and their preferable examples are also the same.
Formula (D-4) will be described in detail.
In Formula (D-4), MD4, LD41, LD42, GD41 and GD42 have the same definitions as corresponding MD1, LD11, LD12, GD11 and GD12 in Formula (D-1) respectively, and their preferable examples are also the same.
XD41, XD42, XD43 and XD44 have the same definitions as corresponding XD21, XD22, XD23 and XD24 in Formula (D-2) respectively, and their preferable examples are also the same. YD41, YD42, YD43 and YD44 have the same definitions as corresponding YD21, YD22, YD23 and YD24 in Formula (D-2) respectively, and their preferable examples are also the same.
Specific examples of the compounds represented by Formula (D-1) are illustrated below, but the invention is not limited thereto.
An example of preferable metal complexes usable in the invention is a compound represented by the following Formula (E-1).
In Formula (E-1), ME1 represents a metal ion. JE11 and JE12 each independently represent an atomic group necessary for forming a 5-membered ring. GE11, GE12, GE13 and GE14 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. YE11, YE12, YE13 and YE14 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
Formula (E-1) will be described in detail.
In Formula (E-1), ME1 has the same definition as MA1 in Formula (A-1), and its preferable examples are also the same. GE11, GE12, GE13 and GE14 have the same definition as GC11 and GC12 in Formula (C-1), and their preferable examples are also the same.
JE11 and JE12 have the same definition as JD11 to JD14 in Formula (D-1), and their preferable examples are also the same. YE11, YE12, YE13 and YE14 have the same definitions as corresponding YC21 to YC24 in Formula (C-2) respectively, and their preferable examples are also the same.
The compound represented by Formula (E-1) is more preferably a compound represented by the following Formula (E-2) or (E-3).
In Formula (E-2), ME2 represents a metal ion. GE21, GE22, GE23 and GE24 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. YE21, YE22, YE23, YE24, YE25 and YE26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
XE21 and XE22 each independently represent an oxygen atom, a sulfur atom, —NRE21— or —C(RE22)RE23—. RE21, RE22 and RE23 each independently represent a hydrogen atom or a substituent.
In Formula (E-3), ME3 represents a metal ion. GE31, GE32, GE33 and GE34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. YE31, YE32, YE33, YE34, YE35 and YE36 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. XE31 and XE32 each independently represent an oxygen atom, a sulfur atom, —NRE31— or —C(RE32)RE33—. RE31, RE32 and RE33 each independently represent a hydrogen atom or a substituent.
Formula (E-2) will be described in detail.
In Formula (E-2), ME2, GE21, GE22, GE23, GE24, YE21, YE22, YE23 and YE24 have the same definitions as corresponding ME1, GE11, GE12, GE13, GE14, YE11, YE12, YE13 and YE14 in Formula (E-1) respectively, and their preferable examples are also the same. XE21 and XE22 have the same definitions corresponding XD21 and XD22 in Formula (D-2) respectively, and their preferable examples are also the same.
Formula (E-3) will be described in detail.
In Formula (E-3), ME3, GE31, GE32, GE33, GE34, YE31, YE32, YE33 and YE34 have the same definitions as corresponding ME1, GE11, GE12, GE13, GE14, YE11, YE12, YE13 and YE14 in Formula (E-1) respectively, and their preferable examples are also the same. XE31 and XE32 have the same definitions as corresponding XE21 and XE22 in Formula (E-2) respectively, and their preferable examples are also the same.
Specific examples of the compounds represented by Formula (E-1) are illustrated below, but the invention is not limited thereto.
An example of metal complexes usable in the invention is a compound represented by the following Formula (F-1).
In Formula (F-1), MF1 represents a metal ion. LF11, LF12 and LF13 each independently represent a connecting group. RF11, RF12, RF13 and RF14 each independently represent a hydrogen atom or a substituent. RF11 and RF12 may, if possible, be bonded to each other to form a 5-membered ring. RF12 and RF13 may, if possible, be bonded to each other to form a ring. RF13 and RF14 may, if possible, be bonded to each other to form a 5-membered ring. QF11 and QF12 each independently represent a partial structure containing an atom bonded to MF1.
The compound represented by Formula (F-1) will be described in detail.
In Formula (F-1), MF1, LF11, LF12, LF13, QF11 and QF12 have the same definitions as corresponding MA1, LA11, LA12, LA13, QA11 and QA12 in Formula (A-1) respectively, and their preferable examples are also the same. RF11, RF12, RF13 and RF14 each independently represent a hydrogen atom or a substituent. RF11 and RF12 may, if possible, be bonded to each other to form a 5-membered ring. RF12 and RF13 may, if possible, be bonded to each other to form a ring. RF13 and RF14 may, if possible, be bonded to each other to form a 5-membered ring. The substituent represented by RF11, RF12, RF13 or RF14 may be selected from the above-mentioned examples of the substituent represented by RC11 to RC14 in Formula (C-1). In a preferable embodiment, RF11 and RF12 are bonded to each other to form a 5-membered ring, and RF13 and RF14 are bonded to each other to form a 5-membered ring. In another preferable embodiment, RF12 and RF13 are bonded to each other to form an aromatic ring.
The compound represented by Formula (F-1) is more preferably a compound represented by Formula (F-2), (F-3) or (F-4).
In Formula (F-2), MF2 represents a metal ion. LF21, LF22 and LF23 each independently represent a connecting group. RF21, RF22, RF23 and RF24 each independently represent a substituent. RF21 and RF22 may, if possible, be bonded to each other to form a 5-membered ring. RF22 and RF23 may, if possible, be bonded to each other to form a ring. RF23 and RF24 may, if possible, be bonded to each other to form a 5-membered ring. ZF21, ZF22, ZF23, ZF24, ZF25 and ZF26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (F-3), MF3 represents a metal ion. LF31, LF32 and LF33 each independently represent a connecting group. RF31, RF32, RF33 and RF34 each independently represent a substituent. RF31 and RF32 may, if possible, be bonded to each other to form a 5-membered ring. RF32 and RF33 may, if possible, be bonded to each other to form a ring. RF33 and RF34 may, if possible, be bonded to each other to form a 5-membered ring. ZF31, ZF32, ZF33 and ZF34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom.
In Formula (F-4), MF4 represents a metal ion. LF41, LF42 and LF43 each independently represent a connecting group. RF41, RF42, RF43 and RF44 each independently represent a substituent. RF41 and RF42 may, if possible, be bonded to each other to form a 5-membered ring. RF42 and RF43 may, if possible, be bonded to each other to form a ring. RF43 and RF44 may, if possible, be bonded to each other to form a 5-membered ring. ZF41, ZF42, ZF43, ZF44, ZF45 and ZF46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. XF41 and XF42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom.
The compound represented by Formula (F-2) will be described in detail.
MF2, LF21, LF22, LF23, RF21, RF22, RF23 and RF24 have the same definitions as corresponding MF1, LF11, LF12, LF13, RF11, RF12, RF13 and RF14 in Formula (F-1) respectively, and their preferable examples are also the same.
ZF21, ZF22, ZF23, ZF24, ZF25 and ZF26 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZF21, ZF22, ZF23, ZF24, ZF25 and ZF26 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1)
The compound represented by Formula (F-3) will be described in detail.
In Formula (F-3), MF3, LF31, LF32, LF33, RF31, RF32, RF33 and RF34 have the same definitions as corresponding MF1, LF11, LF12, LF13, RF11, RF12, RF13 and RF14 in Formula (F-1) respectively, and their preferable examples are also the same. ZF31, ZF32, ZF33 and ZF34 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZF31, ZF32, ZF33 and ZF34 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1)
The compound represented by Formula (F-4) will be described in detail.
In Formula (F-4), MF4, LF41, LF42, LF43, RF41, RF42, RF43 and RF44 have the same definitions as corresponding MF1, LF11, LF12, LF13, RF11, RF12, RF13 and RF14 in Formula (F-1) respectively, and their preferable examples are also the same.
ZF41, ZF42, ZF43, ZF44, ZF45 and ZF46 each independently represent a nitrogen atom or a substituted or unsubstituted carbon atom. Each of ZF41, ZF42, ZF43, ZF44, ZF45 and ZF46 is preferably a substituted or unsubstituted carbon atom, and more preferably an unsubstituted carbon atom. When the carbon atom is substituted, the substituent may be selected from the above-mentioned examples of the substituent on the divalent connecting group represented by LA11, LA12, LA13 or LA14 in Formula (A-1).
XF41 and XF42 each independently represent an oxygen atom, a sulfur atom or a substituted or unsubstituted nitrogen atom. Each of XF41 and XF42 is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
Specific examples of the compounds represented by Formula (F-1) are illustrated below, but the invention is not limited thereto.
Compounds represented by any one of Formulae (A-1) to (F-1) can be synthesized by known methods.
A single kind of metal complex according to the invention may be contained in the composition for an organic EL element, or two or more kinds of metal complex according to the invention may be used in the composition in combination.
The content of metal complex having a tridentate or higher-dentate ligand in the composition for an organic EL element according to the invention is, for example when the composition is used in a luminescent layer, preferably from 0.1 to 70% by mass relative to the total solid content contained in the composition, and more preferably 1 to 20% by mass relative to the total solid content contained in the composition.
Also when forming other organic compound layers and the like than the luminescent layer, the metal complex according to the invention can be used by being contained in an adequate amount in the composition alone or together with other components described below, in accordance with the constitution of each layer.
[Other Components]
The composition for an organic EL element according to the invention may further contain other components than the metal complex according to the invention, in addition to the metal complex. Such additional components form an organic compound layer together with the metal complex.
Examples of organic compound layers that can be formed by applying the composition for an organic EL element according to the invention include a luminescent layer, a charge transport layer, and a charge injection layer. The additional components may be materials contained in such layers.
The composition for an organic EL element according to the invention is preferably dissolved or dispersed in a solvent, so as to prevent the adherence of the solid content in the organic EL composition and clogging caused thereby at the nozzle entrance for the ink jet, so as to contribute to maintenance of a high contact angle of ink at the nozzle entrance, which prevents the ink curve during flight.
Examples of the solvent include water, alcohols such as methanol, ethanol, 1-methoxy-2-propanol, methoxyethanol, and phenoxyethanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, and cyclohexanone, ethers such as dibutyl ether, tetrahydrofuran, and dioxane, esters such as ethyl acetate, butyl acetate, ethyl 2-ethylhexanoate, methyl propionate, ethyl propionate, γ-butyrolactone, and diethyl carbonate, amides such as formamide, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide, aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, and 1,2-dichloroethane, organic solvents such as N-methylpyrrolidone (NMP), dimethylimidazoline (DMI), and dimethylsulfoxide (DMSO), and inorganic solvents. In an embodiment, two or more of these solvents are appropriately mixed, and the mixture is used as the solvent.
Furthermore, the composition preferably contains a lubricant. The lubricant effectively prevents the drying and solidification of the composition at the ink jet nozzle opening. The lubricant may be, for example, a polyhydric alcohol such as glycerin or diethylene glycol. A mixture of two or more lubricants may be used.
The amount of a lubricant to be added is preferably about 5 to 20% by mass relative to the total amount of the composition.
To the composition for an organic EL element, other additives and coated-layer stabilizing materials may be further added, such as stabilizers, viscosity modifiers, antioxidants, pH adjusters, preservatives, resin emulsions, and leveling agents.
The composition for an organic EL element according to the invention is used for pattern formation by an ink jet method.
Here, the pattern formation by an ink jet method refers to a process in which the composition for an organic EL element is dissolved or dispersed in a solvent to form a discharge liquid, and the discharge liquid is discharged from the head of an ink jet apparatus to form pixels of at least one color selected from the three primary colors (e.g., red, green, and blue) and intermediate colors therebetween.
According to this ink jet method, fine patterning can be conducted easily in a short time. Furthermore, because the film thickness can be easily adjusted by increasing or decreasing the discharging amount, the film properties and the coloring performance, such as coloring balance and brightness can be controlled easily and freely.
The viscosity of the composition for an organic EL element according to the invention is preferably from 1 mPa·s to 20 mPa·s, and more preferably from 2 mPa·s to 4 mPa·s. When the viscosity of the composition for an organic EL element is less than 1 mPa·s, the resultant coloring layer does not exhibit sufficient coloring performance in some cases. On the other hand, when the viscosity of the composition for an organic EL element is over 20 mmPa·s, the composition cannot be discharged smoothly from the nozzle opening, and thus, in some cases, patterning is difficult unless the specifications of the device are changed, (for example, enlarging the size of the opening of the nozzle. Furthermore, when the viscosity is high, the solid content in the composition easily precipitates, thus increasing the frequency of occurrence of clogging of the nozzle opening.
Furthermore, the surface tension of the composition for an organic EL element according to the invention may be from 20 mN/m to 70 mN/m, and is preferably from 25 mN/m to 40×10−3 N/m. The curve of the flight path is suppressed and the frequency of the flight path curve can be reduced by making the surface tension within this range, as the case of the contact angle mentioned above. When the surface tension is less than 20 mN/m, the wettability of the composition with respect to the constituent material of the nozzle surface is increased; therefore, in some cases, the flight curve occurs and similarly to the case of the contact angle, and the frequency of the flight curve is high. Furthermore, when the surface tension is over 70 mN/m, the meniscus form at the nozzle tip is not stabilized, and the control of the discharging amount and discharge timing of the composition is difficult in some cases.
Furthermore, the composition for an organic EL element according to the invention preferably has a viscosity and a surface tension, at least one of which meets the above-mentioned range. The composition may meet any combination of two or more conditions of the characteristics, or may meet all of the conditions of the characteristics. Such a composition is more suitable for ink jet methods.
Furthermore, the composition for an organic EL element according to the invention may be prepared as a polymer dispersion liquid that contains a polymer for dispersing a metal complex having the above-mentioned tridentate or higher-dentate ligand. When the composition is in the form of a polymer dispersion liquid, each component of an organic compound layer is preferably dispersed in the polymer. By dispersing the components of the organic compound layer in the polymer, the stability of the components of the organic compound layer in the dispersion liquid is improved, so that an organic electroluminescent element with further improved luminous efficiency and durability can be obtained.
Examples of polymers usable for the dispersion include polyvinyl carbazole, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, and polyvinyl acetal. Only one polymer may be used, or two or more polymers may be used in combination. A luminescent layer containing a polymer binder can be easily formed on a large area through coating by a wet-film forming method. In particular, the polymers described in, for example, JP-A Nos. 2001-11568, 2002-25779, 2004-152746, can be suitably used.
The polymer dispersion liquid can be prepared as follows: a polymer (for example, PVK) and a metal complex according to the invention are dissolved or dispersed in a solvent (for example, a 1:1 mixture of toluene and chloroform) with a dispersing apparatus under stirring for a necessary time for the dissolution or dispersing. The dispersing apparatus is not particularly limited, and a known device can be used.
[Method for Manufacturing an Organic Electroluminescent Element, and the Organic Electroluminescent Element Manufactured by the Method]
Next, the method for manufacturing an organic electroluminescent element according to the invention and the organic electroluminescent element manufactured by the method will be described in detail.
The first embodiment of the method for manufacturing an organic electroluminescent element in the invention includes forming a first electrode on a substrate, discharging the composition according to the invention in a pattern onto the surface (film-forming surface) of the substrate having the first electrode thereon by an ink jet apparatus to form an organic compound layer, and forming a second electrode on the organic compound layer. In the following, the method for manufacturing the organic electroluminescent element in this embodiment will be occasionally referred to as “the method (1) for manufacturing an organic EL element”.
In the method (1) for manufacturing an organic EL element according to the invention, because the deterioration of the composition for an organic EL element held in the ink jet apparatus is suppressed by the use of the composition for an organic EL element according to the invention with excellent stability over time, an organic electroluminescent element having high luminous efficiency and luminance and excellent durability can be manufactured stably and easily.
Furthermore, in the method (1) for manufacturing an organic EL element, because the organic compound layer is formed by an ink jet apparatus, highly fine patterning is possible, and the luminescent property of the obtained element, the film properties of the formed organic compound layer, and the like can be controlled easily.
An example of ink jet apparatuses that can be used suitably in the method (1) for manufacturing an organic EL element will be described.
In such an ink jet apparatus, first, information on the pattern to be formed on the film-forming surface is supplied from an information supply source, such as a computer, to the ink jet recording apparatus through a transmission unit, such as a bus.
The ink jet apparatus may be an apparatus that has a head capable of discharging the droplets of the composition for an organic EL element, and a control system that drives the head according to an arbitrary pattern. The composition is provided on the film-forming surface according to the pattern information by discharging the droplets of the composition for an organic EL element from the nozzle opening (discharge opening) of the head of the apparatus moving according to the pattern information, to a prescribed position on the film-forming surface.
The head installed in the ink jet apparatus is equipped with a cavity that is configured to be filled with the composition for an organic EL element. A voltage corresponding to an arbitrary pattern is applied to the piezoelectric element that is configured to be able to cause a volume change of the cavity, so that the inside volume of the cavity is changed; as a result, the composition for an organic EL element stored in the cavity is supplied in the form of minute droplets from the discharge opening onto the film-forming surface in a prescribed pattern, and is adsorbed on the film-forming surface. Thereafter, the solvent and the dispersion medium in the composition for an organic EL element are removed to form an organic compound layer.
In the invention, besides the above-mentioned method, heads using other principles are naturally usable.
Though the embodiment of the method (1) for manufacturing an organic EL element will be described by taking one example, the invention is not limited to the example.
(1) On a substrate (a glass substrate or the like), pixel electrodes (ITO electrodes or the like) are formed in a pattern by photolithography or the like. A partition wall serving both as a light shielding layer and an ink dripping preventing wall is formed between the pixel electrodes by photolithography or the like.
(2) The composition for an organic EL element for forming a desired organic compound layer is discharged in a pattern from the nozzle opening of the ink jet apparatus to deposit the composition for an organic EL element on the film-forming surface. Then, the solvent or the dispersion medium contained in the composition is removed by a heating treatment or the like, to form the organic compound layer. The organic compound layer to be formed may be a single layer including only a luminescent layer, or may have a laminated structure composed of two or more organic compound layers including a luminescent layer.
In the invention, at least one of the organic compound layers is formed by an ink jet method using the composition for an organic EL element according to the invention. When the organic compound layers have a laminated structure, all the layers including the layer formed by using the compound for the organic EL element according to the invention may be formed by an ink jet method, or some (but not all) of the layers may be formed by other methods involving a deposition method or the like.
(3) Counter electrodes are further formed on the organic compound layer by using a deposition method or the like to give an organic EL element.
(An organic EL element manufactured by using the method (1) for manufacturing an organic EL element)
The first embodiment (hereinafter, it will be suitably referred to as “the organic EL element (1)”) of the organic electroluminescent element according to the invention is manufactured by using the above-mentioned method (1) for manufacturing an organic EL element. The organic EL element (1) preferably has two or more organic compound layers including a luminescent layer. At least one of the organic compound layers is formed by using the composition for an organic EL element according to the invention by the method (1) for manufacturing an organic EL element according to the invention.
The organic EL element according to the invention preferably has two or more organic compound layers including a luminescent layer. In the following, the organic EL element (1) will be described in detail.
The organic EL element (1) according to the invention has a cathode and an anode on the substrate, and has organic compound layers, including a luminescent layer, between the both electrodes. In consideration of the property of the luminescent element, at least one of the anode and the cathode is preferably transparent.
As the mode of the lamination of the organic compound layers in the organic EL element (1), a lamination in the order of a hole transport layer, a luminescent layer, and an electron transport layer from the anode side is preferable. The organic EL element (1) may further have a charge block layer or the like between the hole transport layer and the luminescent layer, and/or between the luminescent layer and the electron transport layer. The organic EL element (1) may have a hole injection layer between the anode and the hole transport layer, and/or may have an electron injection layer between the cathode and the electron transport layer. The organic EL element (1) may have only one luminescent layer, or the luminescent layer may be divided, for example into the first luminescent layer, the second luminescent layer, and the third luminescent layer. Furthermore, each layer may be divided into plural sub-layers.
<Luminescent Layer>
When an electric field is applied to the luminescent element, holes injected from the anode, the hole injection layer, or the hole transport layer, and electron injected from the cathode, the electron injection layer, or the electron transport layer recombine in the luminescent layer to emit light. The material constituting the luminescent layer is not particularly limited as long as the material can form a layer having, upon application of an electric field, the function of receiving holes from the anode or the like, the function of receiving electrons from the cathode or the like, the function of moving charges, and the function of offering a field for the recombination of the holes and the electrons to emit light.
The luminescent layer in the organic EL element (1) is preferably formed by using the composition for an organic EL element according to the invention by the above-mentioned manufacturing method (1) according to the invention.
The luminescent layer in the organic EL element (1) preferably contains a metal complex having a tridentate or higher-dentate ligand. Since the metal complex has a function (A) as a luminescent material, a function (B) as a host material (hereinafter occasionally referred to as “the charge transport material”), and the like, embodiments using each function are preferable.
When the above-mentioned metal complex is used as one having the function (A) other luminescent materials than the metal complex may be further used, such as a material that emits light from either a singlet exciton or a triplet exciton. Examples of such additional luminescent materials include benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, dipnenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perynone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bis-styrylanthracene, quinacridon, pyrrolopyridine, thiadiazolopyridine, styrylamine, aromatic dimethylidyne compounds, metal complexes other than the metal complexes according to the invention (metal complexes of 8-quinolinol derivatives, rare earth complexes, and the like), polymer luminescent materials (polythiophene, polyphenylene, polyphenylene vinylene, and the like), organic silane compounds, transition metal complexes other than the metal complexes according to the invention (iridium trissphenylpyridine complex and the like), and derivatives thereof. Furthermore, cyanine dyes, melocyanine dyes, styryl dyes, dyes of anthracene derivatives, porphyrin derivatives, phthalocyanine derivatives, coumarin, DCM, Nile Red, and the like, laser dyes, and the like, which are other than those mentioned above, can be used.
The content of a luminescent compound in the luminescent layer in the organic EL element (1) is not particularly limited, and is preferably, for example, 0.1 to 70% by mass, and more preferably 1 to 20% by mass. When the content of the luminescent compound is less than 0.1% by mass or over 70% by mass, the effects may be not exhibited sufficiently.
The thickness of the luminescent layer in the organic EL element (1) is preferably from 10 to 200 nm, and more preferably from 20 to 80 nm. When the thickness is over 200 nm, the drive voltage may be increased. On the other hand, when the thickness is less than 10 nm, the organic EL element may be short-circuited.
The drying condition of the thin film can be suitably selected in accordance with the conditions such as the compound and solvent to be used. The drying can be carried out generally under the atmospheric pressure or reduced pressure.
The luminescent layer in the organic EL element (1) may be formed of a single material or of plural materials, as mentioned above. Furthermore, the luminescent layer may be one layer or plural layers. When their are plural luminescent layers, each of the layers may emit light in different color such that white color or the like is emitted. When there are plural luminescent layers, each of the luminescent layers may be formed of a single material, or of plural materials.
Besides the luminescent layer mentioned above, as for other components of the organic EL element (1) such as the substrate, the electrodes, other organic compound layers, and still other layers, for example, those described in [00131] to [0082] of JP-A No. 2004-221068, [0017] to [0091] of JP-A No. 2004-214178, [0024] to [0035] of JP-A No. 2004-146067, [0017] to [0068] of JP-A No. 2004-103577, [0014] to [0062] of JP-A No. 2003-323987, [0015] to [0077] of JP-A No. 2002-305083, [0008] to [0028] of JP-A No. 2001-172284, [0013] to [0075] of JP-A No. 2000-186094, [0016] to [0118] of Japanese Patent Application National Publication (Laid-Open) No. 2003-515897, and the like can be applied in the invention. However, the invention should not be limited to these.
In the hole injection layer and/or the hole transport layer in the organic EL element (1), an electron receiving dopant can be contained. The electron receiving dopant to be introduced into the hole injection layer or the hole transport layer may be an inorganic compound or an organic compound as long as the compound has electron receiving property and is capable of oxidizing organic compounds.
Specific examples of inorganic electron receiving dopants include halogenated metals such as ferric oxide, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide.
Specific examples of organic electron receiving dopants include compounds having a nitro group, a halogen, a cyano group, a trifluoromethyl group, or the like as a substituent, quinone compounds, acid anhydride compounds, and fullerene.
Besides these, compounds described in JP-A Nos. 6-212153, 11-111463, 11-251067, 2000-196140, 2000-286054, 2000-315580, 2001-102175, 2001-160493, 2002-252085, 2002-56985, 2003-157981, 2003-217862, 2003-229278, 2004-342614, 2005-72012, 2005-166637, 2005-209643, and the like can be suitably used.
Only one electron receiving dopant may be used, or two or more electron receiving dopants may be used in combination. The amount of the electron receiving dopant to be used varies depending on the kind of the material, and is preferably from 0.01% by mass to 50% by mass relative to the mass of the hole injection layer material or the hole transport layer material, more preferably from 0.05% by mass to 20% by mass, and particularly preferably from 0.1% by mass to 10% by mass.
In the electron injection layer and/or the electron transport layer in the organic EL element (1), an electron-donating dopant can be contained.
A substance that donates an electron and reduces an organic compound may be used as the electron-donating dopant to be introduced into the electron injection layer or the electron transport layer. Preferable examples thereof include alkali metals such as Li, alkaline-earth metals such as Mg, transition metals containing a rare-earth metal, and reducing organic compounds. As the metal, metals having a work function of 4.2 eV or less can be suitably used. Specific examples thereof include Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd, and Yb. Furthermore, examples of reducing organic compounds include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
Besides these, the materials described in JP-A Nos. 6-212153, 2000-196140, 2003-68468, 2003-229278, 2004-342614 and the like, are also usable as electron-donating dopants.
Only one electron-donating dopant may be used, or two or more electron-donating dopants may be used in combination. The amount of the electron-donating dopant to be used varies depending on the kind of the material, and is preferably from 0.1% by mass to 99% by mass relative to the electron injection layer material or the electron transport layer material, more preferably from 1.0% by mass to 80% by mass, and particularly preferably from 2.0% by mass to 70% by mass.
The second embodiment of the method for manufacturing an organic electroluminescent element in the invention includes forming a first electrode on a substrate, superposing a transfer material having an organic compound layer containing a metal complex having a tridentate or higher-dentate ligand provided on a temporary support, on the side of the substrate that has the first electrode thereon, applying heat and/or pressure thereto, peeling away the temporary support so as to transfer the organic compound layer onto the side of the substrate that has the first electrode thereon (the above processes will be occasionally referred to as “transfer process”), and forming a second electrode on the organic compound layer. In the following, the method for manufacturing the organic electroluminescent element in this embodiment will be occasionally referred to as “the method (2) for manufacturing an organic EL element”.
In the method (2) for manufacturing an organic EL element according to the invention, an organic EL element having high luminous efficiency and luminance and excellent durability can be manufactured stably by the formation of an organic compound layer containing a metal complex having a tridentate or higher-dentate ligand by the peel and transfer method using the transfer material.
The metal complex in the invention is a compound that is excellent in stability under heat and/or pressure. Therefore, an organic EL element having excellent performance can be manufactured even when heat and/or pressure is applied at transfer of the organic compound layer onto the film-forming surface of the substrate. Furthermore, the above-mentioned metal complex is a compound that is excellent in stability in a liquid. Therefore, deterioration with time in the manufacturing process is small even when the transfer layer (the organic compound layer) is formed by a wet method, so that an organic EL element having excellent performance can be manufactured.
[Transfer Material]
First, the transfer material used in the method (2) for manufacturing an organic EL element will be described in detail.
The transfer material can be manufactured by forming an organic compound layer on a temporary support.
In the method (2) for manufacturing an organic EL element, the organic compound layer containing a metal complex having a tridentate or higher-dentate ligand is formed by using the transfer material that has the organic compound layer. Other organic compound layers than the organic compound layer containing the metal complex may also be formed by using a transfer material. Detailed description on the transfer will be described later.
The transfer material can be manufactured by appropriately using known methods, such as a deposition method or a wet method. It is preferable to use a wet method from the viewpoint of the productivity.
In an embodiment, separate transfer materials each having an organic compound layer are prepared independently. In another embodiment, organic compound layers are provided sequentially to form a single transfer material. That is, for example, plural organic compound layers including an organic compound layer that contains a metal complex having a tridentate or higher-dentate ligand may be prepared on a single temporary support. When such a transfer material is used, plural organic compound layers can be consecutively formed without the need for exchanging the transfer material.
Further, when a transfer material in which two or more organic compound layers are laminated in advance on a temporary support is used, the plural layers can be laminated on the film-forming surface of the substrate in a single transfer process. For example, plural organic compound layers including an organic compound layer that contains a metal complex having a tridentate or higher-dentate ligand may be laminated on a temporary support. However, when the plural layers are laminated in advance on the temporary support, the interface of each organic compound layer to be laminated should be uniform; otherwise, the movement of holes and electrons becomes nonhomogenous. In order to make the interface of each organic compound layer uniform, the solvent should be selected carefully. Furthermore, an organic compound that is soluble in the solvent for the organic compound layer should be selected.
<Temporary Support>
The temporary support used in the invention is preferably composed of a material that is chemically and thermally stable and flexible. Specifically, preferable examples thereof include thin sheets of fluororesins [for example, tetrafluoroethylene resin (PTFE) and chlorotrifluoroethylene resin (PCTFE)], polyesters [for example, polyethylene terephthalate and polyethylene naphthalate (PEN)], polyallylate, polycarbonate, polyolefin [for example, polyethylene and polypropylene], polyether sulfone, and the like, and lamination of such sheets. The thickness of the temporary support may suitably be from 1 μm to 300 μm, more preferably from 3 μm to 200 μm, and particularly preferably from 3 μm to 50 μm.
<Formation of the Organic Compound Layer on the Temporary Support>
The organic compound layer can be formed on the temporary support by appropriately applying known methods such as deposition methods and wet methods, and is preferably formed by a wet method such as a coating method or a printing method.
When the organic compound layer containing a metal complex according to the invention is formed by a wet method, it is preferable to form the layer by using a liquid containing the metal complex.
The coating method is not particularly limited as long as the method enables formation of an organic compound layer with a uniform dry film thickness of preferably 200 nm or less, and may be selected from spin coat methods, gravure coating methods, dip coating methods, casting methods, die coating methods, roll coating methods, bar coating methods, extrusion coating methods, and inkjet coating methods. Among them, an extrusion coating method with roll-to-roll that achieves high productivity is preferable.
As the printing method, for example, the screen printing methods, the offset printing methods, the letterpress methods, the gravure printing methods, and the like described in JP-A Nos. 2001-52872, 2001-76874, 2001-93668, 2001-155858, 2001-155861, and the like, can be used.
Examples of organic compound layers that can be formed on the temporary support include, specifically, a luminescent layer, an electron transport layer, a hole transport layer, an electron injection layer, and a hole injection layer having unique characteristics.
The organic compound layer containing metal complexes having a tridentate or higher-dentate ligand, which is formed in the invention, may be selected from a luminescent layer, a charge transport layer, and a charge injection layer, and is preferably a luminescent layer.
Furthermore, various layers for improving the coloring property of the organic compound layer can be cited. Specific examples of compounds used in each layer are described, for example, in an extra issue “Organic EL Display” of “Monthly Display” October, 1998 (Techno Times Corp.), and the like.
In the following, each component of the organic compound layers that can be formed on the temporary support will be described in detail.
—Metal Complex Having a Tridentate or Higher-Dentate Ligand —
The metal complex having a tridentate or higher-dentate ligand contained in the organic compound layer is the same as the metal complex having a tridentate or higher-dentate ligand already described in the description of the composition for an organic EL element according to the invention.
The content of the metal complex having a tridentate or higher-dentate ligand in the organic compound layer varies depending on the kind of the layer containing the metal complex. A preferable content is the content described in the description of the each layer.
—Luminescent Layer—
The organic compound layers include at least one luminescent layer. The luminescent layer contains at least one luminescent compound (luminescent material). The metal complex having a tridentate or higher-dentate ligand according to the invention is preferably contained in the luminescent layer as a luminescent compound.
The luminescent compound is not particularly limited, and may be a fluorescent compound or a phosphorescent compound. Further, a fluorescent compound and a phosphorescent compound may be used at the same time. In the invention, it is preferable to use a phosphorescent compound in view of luminance and luminous efficiency. Hereinafter, the term “derivative” means the compound itself and its derivatives.
As luminescent compounds that can be used in the luminescent layer, besides metal complexes having a tridentate or higher-dentate ligand according to the invention, for example, other fluorescent compounds or phosphorescent compounds listed in the following can be used.
Examples of usable fluorescent compounds include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perynone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bis-styrylanthracene derivatives, quinacridon derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, aromatic dimethylidyne compounds, metal complexes other than the metal complexes according to the invention (metal complexes of 8-quinolinol derivatives, rare earth complexes, and the like), polymer luminescent compounds (polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like). Only one fluorescent compound may be used, or a mixture of two or more fluorescent materials may be used.
A phosphorescent compound is preferably a compound that can emit light from a triplet exciton, and ortho-metalation complexes and porphyrin complexes are preferable. Only one phosphorescent compound may be used, or two or more phosphorescent materials may be used in combination.
The ortho-metalation complex mentioned in the invention is a generic name for the group of compounds described in “Organometallic Chemistry, Fundamentals and Applications” written by Akio Yamamoto, pp. 150 and 232, Shokabo Corp. (1982), “Photochemistry and Photophysics of Coordination Compounds” written by H. Yersin, pp. 71 to 77 and 135 to 146, Springer-Verlag Corp. (1987), and the like. The ligands that form an ortho-metalation complex are not particularly limited, and are preferably selected from 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, and 2-phenylquinoline derivatives. These derivatives may have a substituent. Furthermore, these derivatives may have other ligands than the ligands essential for forming the ortho-metalation complexes. As the central metal for forming an ortho-metalation complex, any transition metal can be used. In the invention, rhodium, platinum, gold, iridium, ruthenium, palladium, and the like can be preferably used. An organic thin film layer containing such an ortho-metalation complex is excellent in luminance and luminous efficiency. Specific examples of ortho-metalation complexes are described in JP-A No. 2000-254171.
The ortho-metalation complex used in the invention can be synthesized by the known methods described in literatures such as Inorg. Chem., No. 30, p. 1685 (1991), No. 27, p. 3464 (1988), and No. 33, p. 545 (1994); Inorg. Chim. Acta, No. 181, p. 245 (1991); J. Organomet. Chem., No. 335, p. 293 (1987); and J. Am. Chem. Soc., No. 107, p. 1431 (1985).
The content of the luminescent compound in the luminescent layer is not particularly specified, and is, for example, preferably from 0.1 to 70% by mass, and more preferably from 1 to 20% by mass. When the content of the luminescent compound is less than 0.1% by mass or over 70% by mass, the effect is not exhibited sufficiently in some cases.
In an embodiment, a metal complex having a tridentate or higher-dentate ligand and other luminescent compound are used in combination as luminescent compounds in the luminescent layer.
The luminescent layer may contain a host compound, a hole transport material, an electron transport material, an electrically inert polymer binder, and the like as necessary. A single compound may perform plural functions selected from the functions of these materials. For example, a carbazole derivative functions not only as a host compound, but also functions as a hole transport material.
The host compound is a compound that causes a luminescent compound to emit light through energy transfer from the excited state of the host compound to the luminescent compound. The metal complex according to the invention can be contained as a host compound in the luminescent layer.
Examples of host compounds that can be applied to the invention include, besides the metal complexes according to the invention, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidyne compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyranedioxide derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyrylpyrazine derivatives, heterocyclic tetracarboxylic acid anhydrides (such as naphthalene tetracarboxylic acid anhydride and perylene tetracarboxylic acid anhydride), phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanine, metal complexes having benzoxazole, benzothiazole, or the like as a ligand, conductive polymers such as polysilane compounds, poly(N-vinylbarbazole) derivatives, aniline copolymers, thiophene oligomers, and polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. Only a single host compound may be used, or two or more host compounds may be used in combination.
The content of the host compound in the luminescent layer is preferably from 0 to 99.9% by mass, and more preferably from 0 to 99.0% by mass.
The hole transport material is not particularly limited as long as the material has any of: the function of injecting holes from the anode, the function of transporting the holes, and the function of blocking the electrons injected from the cathode. The hole transport material may be a low-molecular material or a high-molecular material. Specific examples thereof include the metal complexes according to the invention, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidyne compounds, porphyrin compounds, conductive polymers such as polysilane compounds, poly(N-vinylcarbazole) derivatives, aniline copolymers, thiophene oligomers, and polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. Only a single hole transport material may be used, or two or more hole transport materials may be used. The content of the hole transport material in the luminescent layer is preferably from 0 to 99.9% by mass, and more preferably from 0 to 80.0% by mass.
The electron transport material is not particularly limited as long as the material has any of: the function of injecting electrons from the cathode, the functions of transporting the electrons, and the function of blocking holes injected from the anode. Specific examples thereof include the metal complexes according to the invention, triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyranedioxide derivatives, carbodiimide derivatives, fluorenylidene methane derivatives, distyrylpyrazine derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene tetracarboxylic acid and perylene tetracarboxylic acid, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanine, metal complexes having benzoxazole, benzothiazole, or the like as a ligand, conductive polymers such as aniline copolymers, thiophene oligomers, and polythiophene, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, and polyfluorene derivatives. Only a single electron transport material may be used, or two or more electron transport materials may be used in combination. The content of the electron transport material in the luminescent layer is preferably from 0 to 99.9% by mass, and more preferably from 0 to 80.0% by mass.
When the luminescent layer is formed by a coating method, the layer preferably contains a polymer binder. Examples of polymers that can be used as a polymer binder include polyvinyl carbazole, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, and polyvinyl acetal. Only a single polymer binder may be used, or two or more polymer binders may be used in combination. The luminescent layer having a large area and containing the polymer binder can be easily formed by coating according to a wet film-forming method.
The thickness of the luminescent layer is preferably from 10 to 200 nm, and more preferably from 20 to 80 nm. When the thickness is over 200 nm, the driving voltage may be increased. On the other hand, when the thickness is less than 10 nm, the organic EL element may be short-circuited.
—Hole Transport Layer—
In the invention, it is preferable to provide a hole transport layer comprising the above-mentioned hole transport material, as necessary. The hole transport layer may contain the above-mentioned polymer binder. The thickness of the hole transport layer is preferably from 10 to 200 nm, and more preferably from 20 to 80 nm. When the thickness is over 200 nm, the driving voltage may be increased. When the thickness is less than 10 nm, the organic EL element may be short-circuited.
—Electron Transport Layer—
In the invention, it is preferable to provide an electron transport layer comprising the above-mentioned electron transport material, as necessary. The electron transport layer may contain the above-mentioned polymer binder. The thickness of the electron transport layer is preferably from 10 to 200 nm, and more preferably from 20 to 80 nm. When the thickness is over 200 nm, the driving voltage may be increased. When the thickness is less than 10 nm, the organic electroluminescent element may be short-circuited.
When the organic compound layer is formed by coating according to a liquid phase method, the solvent to be used for preparing the coating liquid through dissolution or dispersion of the material for the organic compound layer is not particularly limited, and may be appropriately selected in consideration of the kind of the component consisting the organic compound layer. Examples of the solvent include water, alcohols such as methanol, ethanol, 1-methoxy-2-propanol, methoxyethanol, and phenoxyethanol, ketones such as acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, and cyclohexanone, ethers such as dibutyl ether, tetrahydrofuran, and dioxane, esters such as ethyl acetate, butyl acetate, ethyl 2-ethylhexanoate, methyl propionate, ethyl propionate, γ-butyrolactone, and diethyl carbonate, amides such as formamide, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide, aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane, and 1,2-dichloroethane, organic solvents such as N-methylpyrrolidone (NMP), dimethylimidazoline (DMI), and dimethylsulfoxide (DMSO), inorganic solvents, and a mixture of two or more of the above solvents. A mixture of solvents selected from these solvents is also usable. The solid content in the coating liquid for an organic compound layer is not particularly limited, and the viscosity can also be arbitrarily selected in accordance with the wet film-forming method to be used.
A process using a bar coating method is described as an example of the formation of an organic compound layer containing the metal complex (the metal complex having a tridentate or higher-dentate ligand) according to the invention on the temporary support by a coating method. However, the preparation method is not limited to this particular example.
(1) First, the metal complex according to the invention is dissolved or dispersed in a solvent to prepare a metal complex containing liquid. The metal complex containing liquid may contain the components of the organic compound layer containing the metal complex.
The metal complex containing liquid is not particularly limited, regardless of whether the liquid is in the form of a solution or a dispersion liquid. The metal complex containing liquid is preferably a polymer dispersion liquid containing a polymer for dispersing the metal complex according to the invention. When the metal complex containing liquid is a polymer dispersion liquid, the components of the organic compound layer containing the metal complex according to the invention is preferably dispersed in the polymer. Since the components of the organic compound layer containing the metal complex are dispersed in the polymer, the stability of the components in the dispersion liquid is improved, whereby an organic EL element with further improved luminous efficiency and durability can be obtained. As the polymer to be used for the dispersing operation, for example, polymers described in JP-A Nos. 2001-11568, 2002-25779, 2004-152746, and the like can be used suitably.
The solvent for dissolving or dispersing the metal complex according to the invention is not particularly limited. The solvents described above as examples of the solvent used for preparing the coating liquid through dissolution or dispersion of the material of the organic compound layer can be used for dissolving or dispersing the metal complex. A mixture of two or more of such solvents is also usable.
The optimum solvent is selected based on the molecular weight, the kind of the substituents, the structure and the like of the metal complex according to the invention.
(2) The metal complex containing liquid obtained above is bar-coated on a temporary support that has been washed in advance, by using a bar coating apparatus (for example, #10, manufactured by Matsubo Corporation, and the like), so that a thin film of the organic compound layer is obtained. A thin film having an arbitrary thickness can be obtained by drying the thin film at room temperature or under heating at atmospheric pressure or reduced pressure.
The drying condition of the thin film can be suitably selected according to the conditions such as the compound and solvent to be used. In general, the drying can be carried out under atmospheric pressure or reduced pressure.
When a polymer dispersion liquid is used as the metal complex containing liquid, dispersion liquids with various viscosities can be used. Because the viscosity of the liquid differs depending on the coating method, it is preferable to prepare a liquid having a suitable viscosity for the coating method.
The polymer dispersion liquid can be prepared by dissolving or dispersing a polymer (for example, PVK) and a metal complex according to the invention in a solvent (for example, a mixture of toluene and chloroform in a ratio of 1:1) by stirring, with a dispersing apparatus, the liquid for a necessary time for the dissolution or dispersion. The dispersion apparatus is not particularly limited, and may be a known apparatus.
The glass transition temperature of the organic compound layer itself or the component in the layer is preferably from 40° C. to (the transfer temperature +40° C.), more preferably from 50° C. to (the transfer temperature +20° C.), and particularly preferably from 60° C. to the transfer temperature. The flow starting temperature of the organic compound layer itself in the transfer material or of the component in the layer is preferably from 40° C. to (the transfer temperature +40° C.), more preferably from 50° C. to (the transfer temperature +20° C.), and particularly preferably from 60° C. to the transfer temperature. The glass transition temperature can be measured with a differential scanning calorimeter (DSC). The flow starting temperature can be measured with, for example, flow tester CFT-500 manufactured by Shimadzu Corporation.
[Manufacture of an Organic EL Element]
In the method (2) for manufacturing an organic EL element, the organic EL element is manufactured as follows: the transfer material described above having an organic compound layer on a temporary support is prepared, the transfer material is placed on the substrate having a first electrode formed thereon such that the organic compound layer side contacts the film-forming surface of the substrate (i.e., the surface having the first electrode), heat and/or pressure is applied, and then the temporary support is peeled away so that the organic compound layer is transferred onto the film-forming surface of the substrate (the peel-transfer method), and a second electrode is formed on the organic compound layer.
When plural organic compound layers are formed, other layers than the organic compound layer containing the metal complex according to the invention can be formed by, besides the peel-transfer method, a dry film-forming method such as a deposition method or a sputtering method, a wet method such as dipping, a spin coat method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, or a gravure coating method, a printing method, or the like.
The peel-transfer method is a method in which the organic compound layer is softened by heating and/or pressurizing the transfer material and is adhered onto the film-forming surface of the substrate, and the temporary support is peeled away to leave only the organic compound layer on the film-forming surface. Furthermore, in the method (2) for manufacturing an organic EL element, the peel-transfer method and the adhesion method may be used together. The adhesion method is a method in which the interfaces of at least two surfaces are bonded to each other by close contact, pressure bonding, fusion bonding, or the like. Specifically, in the method, the organic compound layer transferred onto the film-forming surface, and the substrate having the electrode and/or the organic compound layer formed thereon, are stacked, the organic compound layer is softened by heating and/or pressurizing, and is adhered to the electrode and/or the organic compound layer on the substrate. In the transfer method and the adhesion method used in the invention, heating and pressurizing each may be used alone, or a combination of heat and pressure may be applied.
As a heating device, a generally known method can be used. For example, a laminator, an infrared heater, a roller heater, a laser, a thermal head, and the like can be used. When the transfer of a large area is carried out, a planate heating device is preferable, and a laminator, an infrared heater, a roller heater, and the like are more preferable. The temperature for transfer is not particularly limited, and may be changed according to the material of the organic compound layer and the heating member. In general, the transfer temperature is preferably from 40 to 250° C., more preferably from 50 to 200° C., and particularly preferably from 60 to 180° C. However, the preferable range of the transfer temperature is related to the heat resistance of the heating member, the transfer material, and the substrate, and changes in accordance with the improvement in the heat resistance. The pressurizing device is not particularly limited. When a substrate that is easily destroyed by distortion, such as glass, is used, a device that can apply pressure uniformly is preferred. For example, it is preferable to use a pair of rollers, one or both of which are made of rubber. Specifically, a laminator (trade name: FAST LAMINATOR VA-400 III, manufactured by Taisei Laminator Co., Ltd.) and the like, a heating head for a thermal transfer print, and the like can be used. When pressure is applied, it is preferable that the interfaces uniformly contact with each other. The pressure to be applied is not particularly limited, and, in general, is preferably from 0.1 to 100 MPa, more preferably from 0.1 to 30 MPa, and particularly preferably from 0.1 to 10 MPa.
In the method (2) for manufacturing an organic EL element, the organic EL element can also be formed by laminating plural organic compound layers including the organic compound layer containing at least one metal complex having a tridentate or higher-dentate ligand on the substrate by carrying out repeatedly the processes of transfer and peeling. The plural organic compound layers may have the same composition, or different compositions. When the plural organic compound layers have the same composition, there is an advantage in that omission of the layer caused by transfer defects or peeling defects can be prevented. Furthermore, when different layers are prepared, a design is possible in which the functions are separated and allotted to the different layers, so that the luminous efficiency is improved. For example, in an embodiment, a transparent or opaque conductive layer, a luminescent layer, an electron transport layer, an electron injection layer, and a back electrode are laminated in this order on the film-forming surface by the transfer method. In another embodiment, a transparent conductive layer, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer, and a transparent or opaque back electrode are laminated in this order on the film-forming surface by the transfer method.
The organic compound layer transferred onto the substrate, or a new organic compound layer transferred onto the previously transferred organic compound layer is preferably reheated as necessary. As a result of the reheating, the organic compound layer adheres more tightly to the substrate or to the previously transferred organic compound layer. At the time of reheating, it is preferable to apply pressure as necessary. The reheating temperature is preferably in a range of the transfer temperature ±50° C.
A surface treatment for improving adhesion strength may be performed on the film-forming surface during the previous transfer process and the next transfer process so that the previous transfer layer is not reversely transferred to the next transfer layer. Examples of such a surface treatment include activation treatments such as the corona discharge treatment, the flame treating, the glow discharge treatment, and the plasma processing. When a surface treatment is conducted, the transfer temperature for the previous transfer material may be lower than the transfer temperature for the next transfer material as long as no reverse transfer occurs.
The manufacturing apparatus used in the transfer method may have an apparatus that feeds a transfer material having an organic compound layer formed on the temporary support, a device that transfers the organic compound layer onto the film-forming surface of the substrate by pushing the transfer material against the film-forming surface of the substrate while heating the transfer material, and a device that peels the temporary support off the organic compound layer after the transfer. The manufacturing apparatus preferably has a device that preheats the transfer material and/or the substrate before supplying them to the transfer device. Furthermore, the apparatus preferably has a cooling device as a stage subsequent to the transfer device.
The apparatus used in the method (2) for manufacturing an organic EL element is not particularly limited. In a preferable example of the apparatus, a glove box whose internal air is replaced with an inert gas such as nitrogen or argon is connected to a deposition device or sputtering device for forming the back electrode, and the formed laminated body can be moved to the next process without exposure to the air.
Furthermore, in the method (2) for manufacturing an organic EL element, each process is preferably conducted in the atmosphere with a moisture content of 100 ppm or less and an oxygen content of 100 ppm or less.
Although suitable embodiments of the method (2) for manufacturing an organic EL element will be described, the embodiments should not be construed as limiting the invention.
First, a coating liquid is prepared by dissolving or dispersing the material of the organic compound layer containing the metal complex according to the invention in a glove box whose internal air has been substituted with an inert gas (nitrogen, argon, or the like) whose moisture content is 100 ppm or less and whose oxygen content is 100 ppm or less. The coating liquid is applied on a temporary support with a spin coater or the like in the glove box, and the resultant organic compound layer is dried to form a transfer material. Furthermore, transfer materials for forming organic compound layers not containing the metal complex according to the invention can be manufactured in a similar manner.
Separately, a substrate support is placed in a vacuum chamber of a deposition device connected to the glove box, and a transparent or opaque electrode is formed on the substrate support. Next, the substrate having a transparent or opaque electrode formed thereon is moved into the glove box. Then, the transfer material is superposed on the substrate such that the organic compound layer side of the transfer material contacts the film-forming surface of the substrate and is heated and/or pressurized, and then the organic compound layer is transferred onto the film-forming surface of the substrate by peeling away the temporary support. Next, in order to form a transparent or opaque back electrode, the substrate is moved into the deposition device connected to the glove box, and a transparent or opaque back electrode is formed. The obtained laminated body is returned to the glove box again, and the electrode and the back electrode each are connected to an aluminum lead wire. Further, sealing is conducted with a sealant, so that an organic EL element is obtained.
(Organic EL Element Manufactured by Using the Method (2) for Manufacturing an Organic EL Element)
The organic electroluminescent element according to the first embodiment of the invention is manufactured by using above-mentioned method (2) for manufacturing an organic EL element (hereinafter occasionally referred to as “the organic EL element (2)”).
[Whole Structure of the Element]
The whole structure of the organic EL element (2) may be a structure having the following layers and electrodes in this order on a substrate support:
a transparent or opaque conductive layer-a luminescent layer-a back electrode,
a transparent conductive layer-a luminescent layer-an electron transport layer-a transparent or opaque back electrode,
a transparent or opaque conductive layer-a hole transport layer-a luminescent layer-an electron transport layer-a transparent or opaque back electrode,
a transparent or opaque conductive layer-a hole transport layer-a luminescent layer-a transparent or opaque back electrode,
a transparent or opaque conductive layer-a luminescent layer-an electron transport layer-an electron injection layer-a transparent or opaque back electrode,
a transparent or opaque conductive layer-a hole injection layer-a hole transport layer-a luminescent layer-an electron transport layer-an electron injection layer-a transparent or opaque back electrode.
Structures in which the above layers are disposed in the reverse order are also usable. In the organic EL element (2), luminescence is usually taken out from the transparent conductive layer.
<Organic Compound Layer>
The description above about the organic compound layers that can be formed on a temporary support is also applicable to the organic compound layers of the organic EL element (2).
—Patterning—
A mask (a fine mask) having openings in a fine pattern may be used for the formation of a finely patterned organic compound layer. The material of the mask is not limited, and is preferably a durable and cheap material, such as metals, glass, ceramics, and heat-resistant resins are preferable. A combination of one or more of these materials is also usable. From the viewpoints of mechanical strength and the transfer accuracy of the organic compound layer, the thickness of the mask is preferably from 2 to 100 μm, and more preferably from 5 to 60 μm.
The openings in the mask are preferably tapered such that the opening is larger at the transfer material side than the substrate side, so as to allow the organic compound layer of the transfer material to adhere accurately to the transparent conductive layer or different organic compound layer on which the organic compound layer is to be formed according to the shape of the openings of the mask.
In another preferable patterning method, the surface of the transfer material on which concave and convex patterns are formed is superposed on a substrate, and the organic compound layer formed in the convex region of the transfer material is transferred onto the substrate. The pattern corresponding to the concavity and convexity of a pushing member can be formed on the surface of the transfer material by pushing the pushing member, having thereon a prescribed pattern of concavity and convexity, against the surface of the organic compound layer provided on the temporary support of the transfer material. Plural transfer materials each having an organic compound layer of a different composition may be formed. Therefore, a patterned organic compound layer having plural organic compound layers with different compositions formed thereon can be manufactured by repeating the transfer onto the substrate, using such plural transfer materials.
[Other Constituent Elements]
Concerning other constituent elements such as the substrate, the electrode, other organic layers, and other layers in the organic EL element according to the invention, besides those already described, for example, those described in [0013] to [0082] of JP-A No. 2004-221068, [0017] to [0091] of JP-A No. 2004-214178, [0024] to [0035] of JP-A No. 2004-146067, [0017] to [0068] of JP-A No. 2004-103577, [0014] to [0062] of JP-A No. 2003-323987, [0015] to [0077] of JP-A No. 2002-305083, [0008] to [0028] of JP-A No. 2001-172284, [0013] to [0075] of JP-A No. 2000-186094, [0016] to [0118] of Japanese Patent Application National Publication (Laid-Open) No. 2003-515897, and the like can be applied similarly in the invention. However, the constituent elements usable in the invention are not limited to these.
In the hole injection layer and/or the hole transport layer in the organic EL element (2), an electron receiving dopant can be contained. The electron receiving dopant to be introduced into the hole injection layer or the hole transport layer may be an inorganic compound or an organic compound as long as the compound has properties of receiving an electron and of oxidizing organic compounds.
Specifically, the inorganic compound may be, for example, a halogenated metal such as ferric oxide, aluminum chloride, gallium chloride, indium chloride, or antimony pentachloride, or a metal oxide such as vanadium pentoxide or molybdenum trioxide.
The organic compound may be, for example, a compound having a nitro group, a halogen, a cyano group, a trifluoromethyl group, or the like as a substituent, a quinone compound, an acid anhydride compound, or a fullerene.
Besides these, compounds described in JP-A Nos. 6-212153, 11-111463, 11-251067, 2000-196140, 2000-286054, 2000-315580, 2001-102175, 2001-160493, 2002-252085, 2002-56985, 2003-157981, 2003-217862, 2003-229278, 2004-342614, 2005-72012, 2005-166637, 2005-209643, and the like can be suitably used.
Only one electron receiving dopant may be used, or two or more electron receiving dopants may be used. The amount of the electron receiving dopant to be used varies depending on the kind of the material, and is preferably from 0.01% by mass to 50% by mass relative to the hole injection layer material or the hole transport layer material, more preferably from 0.05% by mass to 20% by mass, and particularly preferably from 0.1% by mass to 10% by mass.
In the electron injection layer and/or the electron transport layer in the organic EL element (2), an electron-donating dopant can be contained.
The electron-donating dopant introduced into the electron injection layer or the electron transport layer has properties of donating an electron and of reducing organic compounds. The electron-donating dopant is preferably an alkali metal such as Li, an alkaline-earth metal such as Mg, a transition metal (whose scope includes rare-earth metals), a reducing organic compound, or the like. As the metal, metals having a work function of 4.2 eV or less can be suitably used in particular. Specific examples include Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd, and Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
Besides these, as an electron-donating dopant, materials described in JP-A Nos. 6-212153, 2000-196140, 2003-68468, 2003-229278, 2004-342614, and the like can be used.
Only a single electron-donating dopant may be used, or two or more electron-donating dopants may be used in combination. The amount of the electron-donating dopant to be used varies depending on the kind of the material, and is preferably from 0.1% by mass to 99% by mass relative to the electron injection layer material or the electron transport layer material, more preferably from 1.0% by mass to 80% by mass, and particularly preferably from 2.0% by mass to 70% by mass.
The organic EL elements (1) and (2) emit light when a direct current (, which may include an alternating current component as necessary) voltage (usually from 2 V to 15 V) or direct current is applied between the anode and the cathode.
As for the driving method of the organic EL elements (1) and (2), the driving methods described in JP-A Nos. 2-148687, 6-301355, 5-29080, 7-134558, 8-234685, and 8-241047, Japanese Patent No. 2784615, and U.S. Pat. Nos. 5,828,429 and 6,023,308 can be applied.
The organic EL elements (1) and (2) can be suitably used in display elements, displays, backlights, electrophotography, illumination light sources, light sources for recording, light sources for exposing, light sources for reading, marks, signboards, interiors, optical communication, and the like.
In the following, illustrative embodiments according to the invention will be described.
<1> A composition for an organic electroluminescent element capable of forming a pattern by an ink jet method, comprising at least one metal complex having a tridentate or higher-dentate ligand.
<2> The composition according to <1>, wherein the tridentate or higher ligand is a chain ligand.
<3> The composition according to <1> or <2>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (I).
In Formula (I), M11 represents a metal ion; L11 to L15 each independently represent a ligand coordinated to M11; in no case does an additional atomic group connect L11 and L14 to form a cyclic ligand; in no case, is L15 bonded to both L11 and L14 to form a cyclic ligand; Y11 to Y13 each independently represent a connecting group, a single bond, or a double bond; when Y11, Y12, or Y13 represent a connecting group, the bond between L11 and Y12, the bond between Y12 and L12, the bond between L12 and Y11, the bond between Y11 and L13, the bond between L13 and Y13, and the bond between Y13 and L14 are each independently a single bond or a double bond; and n11 represents an integer of 0 to 4. Each bond connecting M11 and each of L11 to L15 may be selected from a coordinate bond, an ionic bond and a covalent bond.
<4> The composition according to any one of <1> to <3>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (II).
In Formula (II), MX1 represents a metal ion. QX11 to QX16 each independently represent an atom coordinating to MX1 or an atomic group containing an atom coordinating to MX1. LX11 to LX14 each independently represent a single bond, a double bond or a connecting group.
Namely, in Formula (II), the atomic group comprising QX11-LX11-QX12-LX12-QX13 and the atomic group comprising QX14-LX13-QX15-LX14-QX16 each form a tridentate ligand.
In addition, the bond between MX1 and each of QX11 to QX16 may be a coordination bond, an ionic bond, or a covalent bond.
<5> The composition according to <1>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (III).
In Formula (III), Q11 represents an atomic group forming a nitrogen-containing heterocycle; Z11, Z12, and Z13 each represent a substituted or unsubstituted carbon or nitrogen atom; and MY1 represents a metal ion that may further have a ligand.
<6> The composition according to any one of <1> to <5>, comprising a polymer dispersion liquid that contains a polymer for dispersing the metal complex having the tridentate or higher-dentate ligand.
<7> A method for manufacturing an organic electroluminescent element, the method comprising forming a first electrode on a substrate, forming an organic compound layer by discharging the composition of any one of <1> to <6> in a pattern onto the side of the substrate that has the first electrode thereon using an ink jet apparatus, and forming a second electrode on the organic compound layer.
<8> A method for manufacturing an organic electroluminescent element, the method comprising forming a first electrode on a substrate, superposing a transfer material having an organic compound layer containing a metal complex having a tridentate or higher-dentate ligand provided on a temporary support, on the side of the substrate that has the first electrode thereon, applying heat and/or pressure thereto, peeling away the temporary support so as to transfer the organic compound layer onto the side of the substrate that has the first electrode thereon, and forming a second electrode on the organic compound layer.
<9> The method for manufacturing an organic electroluminescent element according to <8>, wherein the organic compound layer containing the metal complex having the tridentate or higher-dentate ligand is formed on the temporary support by using a liquid containing the metal complex having the tridentate or higher-dentate ligand.
<10> The method for manufacturing an organic electroluminescent element according to <8> or <9>, wherein the tridentate or higher-dentate ligand is a chain ligand.
<11> The method for manufacturing an organic electroluminescent element according to any one of <8> to <10>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (I).
In Formula (I), M11 represents a metal ion; L11 to L15 each independently represent a ligand coordinated to M11; in no case does an additional atomic group connect L11 and L14 to form a cyclic ligand; in no case, is L15 bonded to both L11 and L14 to form a cyclic ligand; Y11 to Y13 each independently represent a connecting group, a single bond, or a double bond; when Y11, Y12, or Y13 represent a connecting group, the bond between L11 and Y12, the bond between Y12 and L12, the bond between L12 and Y11, the bond between Y11 and L13, the bond between L13 and Y13, and the bond between Y13 and L14 are each independently a single bond or a double bond; and n11 represents an integer of 0 to 4. Each bond connecting M11 and each of L11 to L15 may be selected from a coordinate bond, an ionic bond and a covalent bond.
<12> The method for manufacturing an organic electroluminescent element according to any one of <8> to <11>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (II).
In Formula (II), MX1 represents a metal ion. QX11 to QX16 each independently represent an atom coordinating to MX1 or an atomic group containing an atom coordinating to MX1. LX11 to LX14 each independently represent a single bond, a double bond or a connecting group.
Namely, in Formula (II), the atomic group comprising QX11-LX11-QX12-LX12-QX13 and the atomic group comprising QX14-LX13-QX15-LX14-QX16 each form a tridentate ligand.
In addition, the bond between MX1 and each of QX11 to QX16 may be a coordination bond, an ionic bond, or a covalent bond.
<13> The method for manufacturing an organic electroluminescent element according to <8> or <9>, wherein the metal complex having the tridentate or higher-dentate ligand is a compound represented by the following formula (III).
In Formula (III), Q11 represents an atomic group forming a nitrogen-containing heterocycle; Z11, Z12, and Z13 each represent a substituted or unsubstituted carbon or nitrogen atom; and MY1 represents a metal ion that may further have a ligand.
<14> The method for manufacturing an organic electroluminescent element according to any one of <8> to <13>, wherein the liquid containing the metal complex containing the tridentate or higher-dentate ligand is a polymer dispersion liquid that contains a polymer for dispersing the metal complex.
<15> An organic electroluminescent element manufactured by using the method for manufacturing an organic electroluminescence element according to any one of <7> to <14>.
In the following, the present invention will be further described in detail by reference to Examples. However, the Examples should not be construed as limiting the invention.
A glass substrate of 25 mm×25 mm×0.7 mm having thereon an ITO film with a thickness of 150 nm (manufactured by Sanyo Vacuum Industries Co., Ltd.) is used as a transparent supporting substrate. This transparent supporting substrate is etched and washed.
After Baytron P (PEDOT-PSS solution (Polyethylene dioxythiophene-polystyrene sulfonate-doped body) manufactured by Bayer AG) for the hole injection and transport layer is spin coated on this ITO glass substrate, the coated layer is dried at 100° C. for one hour under vacuum to form a hole injection and transport layer (about 100 nm in film thickness).
On this layer, a solution for a luminescent layer that contains 0.45% by mass of polyvinyl carbazole (having the structure shown below and a Mn of 25000 to 50000, manufactured by Aldrich Corp.), 0.05% by mass of tris(2-phenylpyridine)iridium complex (ortho-metalation complex), 1% by mass of water, 23.5% by mass of methanol, 60% by mass of DMF, 5% by mass of glycerin, and 10% by mass of diethylene glycol is coated by being discharged from the head of an ink jet printing apparatus, to form a luminescent layer (about 50 nm in film thickness).
Thereafter, Balq and Alq, which are electron transfer materials, are deposited sequentially to thicknesses of 20 nm and 30 nm respectively, so that an electron transport layer is formed.
Furthermore, LiF is deposited to a thickness of about 3 nm in the vacuum of 10−3 to 10−4 Pa with the temperature of the substrate being room temperature.
On this layer, a patterned mask (a mask to give a luminescence area of 2 mm×2 mm) is placed, and then aluminum is deposited to a thickness of about 400 nm, so that an element of Comparative Example 1A is obtained.
The manufactured element is sealed in a dried glove box.
Polyvinyl carbazole
Tris(2-phenylpyridine)iridium complex
An element is manufactured in the same manner as in Comparative Example 1A, except for using a compound (Pt-1) having the following structure in place of tris(2-phenylpyridine)iridium complex used in the element of Comparative Example 1A.
An element is manufactured in the same manner as in Comparative Example 1A, except for using a compound (Ir-1) having the following structure in place of tris(2-phenylpyridine)iridium complex used in the element of Comparative Example 1A.
An element is manufactured in the same manner as in Comparative Example 1A, except for using a compound (Pt-2) having the following structure in place of the compound (Pt-1) used in the element of Example 1A.
<Evaluation of the Elements>
(1) Luminous Efficiency: External Quantum Efficiency
Using a Source Measure Unit 2400 manufactured by KEITHLEY, a direct current voltage is applied to each element to cause emission of light. The luminance is measured with a luminance meter BM-8, manufactured by Topcon Corporation, and the emission spectrum and the emission wavelength are measured with a spectrum analyzer PMA-11, manufactured by Hamamatsu Photonics KK. Based on these measured values, the external quantum efficiency around the luminance of 1000 cd/m2 is calculated according to the luminance conversion method, and is evaluated according to the following criteria.
—Evaluation Criteria—
A: 5% or more
B: 3% or more but less than 5%
C: less than 3%
(2) Driving Durability: Half Life of Luminance
Similarly to (1) above, a direct current voltage is applied to each element to obtain a luminance of 1000 cd/m2, and the time until the luminance reduces to 500 cd/m2 (the half life of luminance) is measured. The results are evaluated according to the following criteria.
—Evaluation Standard—
A: 2000 hours or more
B: 1000 hours or more but less than 2000 hours
C: less than 1000 hours
Table 1 shows the evaluation results, together with the luminescent color of each element.
Elements of Examples 1B and 2B and Comparative Examples 1B and 2B are manufactured in the same manner as in Examples 1A and 2A and Comparative Examples 1A and 2A, respectively, except that the solution for a luminescent layer is coated by being discharged from the head of the ink jet printing apparatus five hours after the preparation thereof.
<Evaluation of the Elements>
(3) External Quantum Efficiency and Half Life of Luminance in the Case the Solutions Undergo Time Passage.
The external quantum efficiency and the half life of luminance of the elements manufactured as described above are measured by the same methods as the above-mentioned methods (1) and (2), respectively.
Table 2 shows the evaluation results, together with the luminescent color of each element.
Elements of Examples 3A and 3B are manufactured in the same manner as in Examples 1A and 1B, respectively, except for using a compound (Pt-3) having the following structure in place of the compound (Pt-1) used in the elements of Examples 1A and 1B.
Furthermore, elements of Comparative Examples 3A and 3B are manufactured manufactured in the same manner as in Comparative Examples 1A and 1B, respectively, except for using a compound (Ir-3) having the following structure as a comparative compound in place of tris(2-phenylpyridine)iridium complex used for manufacturing the elements of Comparative Examples 1A and 1B.
The luminescent colors of the elements of Examples 3A and 3B and Comparative Examples 3A and 3B are blue.
As compared with Comparative Examples 3A and 3B, Examples 3A and 3B are excellent in external quantum efficiency and driving durability in the case where the solutions undergo time passage or does not undergo time passage.
Furthermore, similar elements can be manufactured by using compounds represented by the formula (II) (for example, compound (103), and the like cited above as exemplary compounds) or compounds represented by the formula (III) (for example, compound (64), compound (82), and the like cited above as illustrative compounds) in place of “Pt-1”, “Pt-2”, “Pt-3” used for manufacturing the elements of Examples 1A, 1B, 2A, 2B, 3A, and 3B. Favorable results according to the invention can be achieved also with these elements, similarly to the element of the Examples.
As is apparent from the above results, each of the elements of Examples 1A, 1B, 2A, 2B, 3A, and 3B that are obtained by using the compositions for an organic EL element containing a metal complex having a tridentate or higher-dentate ligand is excellent in luminous efficiency and in driving durability, as compared with the elements of Comparative Examples that are obtained by using a compositions for an organic EL element containing a metal complex having a bidentate ligand. Furthermore, it is understood that the elements manufactured by using a metal complex having a tridentate or higher-dentate ligand are small in deterioration of performance caused by lapse of time after the preparation of the solution, and have suppressed performance variation caused by fluctuation of manufacturing factors, as compared with the elements of Comparative Examples manufactured by using a metal complex having a bidentate ligand.
As described in detail above, according to the invention, it is possible to provide a method for manufacturing an organic electroluminescent element that can stably supply a luminescent element having high luminous efficiency and high driving durability by using a pattern forming method involving an ink jet method.
(1) Manufacture of Substrate A
A glass plate with a thickness of 0.5 mm is cut into 2.5 cm square as a substrate support, and the substrate support is introduced into the vacuum chamber of a deposition device. A transparent electrode (an anode) consisting of ITO thin film with a thickness of 0.2 μm is formed on the substrate support by DC magnetron sputtering (conditions: temperature in the substrate support is 100° C., and oxygen pressure is 1×10−3 Pa) using an ITO target containing 10% by mass of SnO2 (indium:tin=95:5 (molar ratio)). The surface resistance of the ITO thin film is 10 Ω/sq.
Next, the glass plate having the transparent electrode formed thereon is moved into a glove box (whose internal air has been substituted with a nitrogen gas containing 30 ppm of moisture and 30 ppm of oxygen) connected to the deposition device. The transparent electrode (ITO) is connected to an aluminum lead wire to form a laminated structure. The glass plate having the transparent electrode is put in a washing vessel, and is washed with isopropyl alcohol (IPA). Thereafter, the glass plate is subjected to an oxygen plasma treatment. An aqueous dispersion liquid of polyethylene dioxythiophene-polystyrene sulfonate (trade name: BAYTON P, manufactured by Bayer AG; solid content of 1.3% by mass) is spin-coated on the surface of the transparent electrode. Then, the glass plate is placed in the vacuum chamber, which is connected to the glove box, and is dried at 150° C. for two hours under vacuum to form a hole transport layer with a thickness of 100 nm.
(2) Manufacture of Transfer Material M
In the glove box, a coating liquid having the following composition for a luminescent layer is applied onto one surface of a temporary support consisting of polyether sulfone (manufactured by Sumitomo Bakelite Co., Ltd.) having a thickness of 188 μm by using a spin coater, and is dried at room temperature to form a luminescent layer having a thickness of 40 nm on the temporary support.
<Composition of the Coating Liquid for a Luminescent Layer>
Polyvinyl carbazole (Mw=63,000, manufactured by Aldrich Corp.): 40 mass parts
Tris(2-phenylpyridine)iridium complex (ortho-metalation complex): 1 mass part
Dichloroethane: 3200 mass parts
(3) Manufacture of an Organic Electroluminescent Element
The substrate A having the hole transport layer formed thereon is returned into the glove box, and the luminescent layer side of the transfer material M is superposed on the upper surface of the hole transport layer of the substrate A. Heat and pressure are applied thereto by using a pair of heating rollers (160° C., 0.3 MPa, and 0.05 m/minute). And then, a substrate MA having a luminescent layer formed on the upper surface of the hole transport layer is manufactured by peeling the temporary support away. It is confirmed with naked eyes that the luminescent layer is formed uniformly when irradiating ultraviolet rays of 254 nm with a handy type UV lamp (trade name: UVGL-25, manufactured by Funakoshi Co., Ltd.).
The substrate MA having the luminescent layer formed thereon is moved to the deposition device connected to the glove box, and compound A having the following structure is deposited as an electron transport material on the luminescent layer at a rate of 1 nm/second, to prepare an electron transport layer 0.036 μm thick. Furthermore, a patterned mask (a mask to give a luminescent area of 5 mm×5 mm) is placed thereon, and then LiF film (the electron injection layer) having a thickness of 3 nm is formed by a deposition method. Furthermore, Al is deposited to a thickness of 0.3 μm to form a back electrode (cathode), to form a laminated structure.
The obtained laminated structure is returned into the glove box connected to the deposition device, and an aluminum lead wire is connected to the back electrode. Furthermore, the laminated structure is sealed in a glass sealing vessel by using an UV-curable adhesive (trade name: XNR5493, manufactured by Nagase Chiba Co., Ltd.) to make an organic EL element of Comparative Example 4A.
An element is manufactured in the same manner as in Comparative Example 4A, except for using compound (Pt-1) having the following structure in place of tris(2-phenylpyridine)iridium complex used in the element of Comparative Example 4A.
An element is manufactured in the same manner as in Comparative Example 4A, except for using compound (Ir-1) having the following structure in place of tris(2-phenylpyridine)iridium complex used in the element of Comparative Example 4A.
An element is manufactured in the same manner as in Example 4A, except for using compound (Pt-2) having the following structure in place of compound (Pt-1) used in the element of Example 4A.
<Evaluation of the Elements>
(1) Luminous Efficiency: External Quantum Efficiency
Using a Source Measure Unit 2400 manufactured by KEITHLEY, a direct current voltage is applied to each element to cause emission of light. The luminance is measured with a luminance meter BM-8, manufactured by Topcon Corporation, and the emission spectrum and the emission wavelength are measured with a spectrum analyzer PMA-11, manufactured by Hamamatsu Photonics KK. Based on these measured values, the external quantum efficiency around the luminance of 1000 cd/m2 is calculated according to the luminance conversion method, and is evaluated according to the following criteria.
—Evaluation Criteria—
A: 5% or more
B: 3% or more but less than 5%
C: less than 3%
(2) Driving Durability: Half Life of Luminance
A direct current voltage is applied to each element to obtain a luminance of 1000 cd/m2, and the time until the luminance reduces to 500 cd/m2 (the half life of luminance) is measured. The results are evaluated according to the following criteria.
—Evaluation Standard—
A: 2000 hours or more
B: 1000 hours or more but less than 2000 hours
C: less than 1000 hours
Table 3 shows the evaluation results, together with the luminescent color of each element.
Elements of Examples 4B and 5B and Comparative Examples 4B and 5B are manufactured in the same manner as in Examples 4A and 5A and Comparative Examples 4A and 5A, respectively, except that the solution for a luminescent layer is spin-coated five hours after the preparation thereof.
<Evaluation of the Elements>
(3) External Quantum Efficiency and Half Life of Luminance in the Case the Solutions Undergo Time Passage.
The external quantum efficiency and the half life of luminance of the elements manufactured as described above are measured by the same methods as the methods (1) and (2), respectively.
Table 4 shows the evaluation results, together with the luminescent color of each element.
Elements of Examples 6A and 6B are manufactured in the same manner as in Examples 4A and 4B, respectively, except for using compound (Pt-3) having the following structure in place of compound (Pt-1) used in the elements of Examples 4A and 4B.
Furthermore, elements of Comparative Examples 6A and 6B are manufactured in the same manner as in Comparative Examples 4A and 4B, except for using compound (Ir-3) having the following structure as a comparative compound in place of tris(2-phenylpyridine)iridium complex used in the elements of Comparative Examples 4A and 4B.
The luminescent colors of the elements of Examples 6A and 6B and Comparative Examples 6A and 6B are blue.
As compared with Comparative Examples 6A and 6B, Examples 6A and 6B are excellent in external quantum efficiency and driving durability in the case where the solutions undergo time passage or does not undergo time passage.
(1) Manufacture of Substrate B
Polyimide sheets (trade name: UPILEX 50S, 50 μm in thickness, manufactured by Ube Industries, Ltd.) are laminated on both sides of aluminum foil having a thickness of 30 μm by using an adhesive. Then the aluminum foil is put in a washing vessel in a glove box (whose internal air has been substituted with nitrogen gas containing 30 ppm of moisture and 30 ppm of oxygen), and is washed with isopropyl alcohol (IPA). Thereafter, the aluminum foil is subjected to an oxygen plasma treatment. Then, the substrate (i.e., aluminum foil) is moved to a deposition device connected to the glove box. A patterned mask (a mask to give a luminescence area of 5 mm×5 mm) for deposition is placed on one side of the substrate that has been treated with oxygen plasma, and Al is deposited in a reduced-pressure atmosphere of about 0.1 mPa to form a back electrode (cathode) having a thickness of 0.3 μm. Further, as an electron injection layer, LiF is deposited to a thickness of 3 nm in the same pattern as the Al layer. The substrate having the electrode and the electron injection layer formed thereon is moved to the glove box, and an aluminum lead wire is connected to the Al electrode. The substrate is moved again into the deposition device, and the compound A shown above is deposited as an electron transport material on the LiF layer at a rate of 1 nm/second to prepare an electron transport layer having a thickness of 0.036 μm.
(2) Manufacture of Substrate MA
The substrate MA is manufactured by forming a luminescent layer in the same manner as in Examples 4A and 4B.
(3) Manufacture of an Organic Electroluminescent Element
The substrate MA and the substrate B are stacked in the glove box such that the film-forming surface of the substrate MA having the transferred luminescent layer contacts the electron transport layer of the substrate B. The substrate MA and the substrate B are bonded to each other by heat and pressure (160° C., 0.3 MPa) using a pair of heating rollers (0.05 m/minute). Then, an aluminum lead wire is connected to the back electrode to make a laminated structure. Then, the laminated structure is sealed in a glass sealing vessel with an UV-curable adhesive (trade name: XNR5493, manufactured by Nagase Chiba Co., Ltd.), so that organic EL elements of Example 6A and 6B are obtained.
<Evaluation of the Elements>
The obtained elements are evaluated in the same manner as in Examples 4A and 4B. As a result, excellent results similar to Examples 4A and 4B are obtained.
As clearly seen from the above results, each of the elements of Examples 3A, 3B, 4A, 4B, 5A, 5B, 6A, 6B, 7A, and 7B in which metal complexes having a tridentate or higher-dentate ligand are used is excellent in luminous efficiency and driving durability, as compared with the elements of Comparative Examples in which metal complexes having a bidentate ligand are used. Furthermore, it is understood that the performance of the elements of Comparative Examples in which conventional metal complexes having a bidentate ligand is deteriorated with lapse of time in the solution state, while each of the elements of Examples exhibits smaller deterioration of performance after time passage in the solution state and can suppress the variation of performance caused by fluctuation of manufacturing factors.
Furthermore, similar elements can be manufactured by using compounds represented by the formula (II) (for example, compound (103), and the like cited above as exemplary compounds) or compounds represented by the formula (III) (for example, compound (64), compound (82), and the like cited above as illustrative compounds) in place of “Pt-1”, “Pt-2”, “Pt-3” used for manufacturing the elements of Examples 4A, 4B, 5A, 5B, 6A, 6B, 7A, and 7B. Favorable results according to the invention can be achieved also with these elements, similarly to the element of the above Examples.
As described in detail above, according to the invention, a method for manufacturing an organic electroluminescent element is provided which can stably supply a luminescent element having high luminous efficiency and high driving durability by using a simple liquid phase method. Furthermore, the organic electroluminescent element can be manufactured at high productivity and low cost by the use of the peel-transfer method (or, the peel-transfer method and the adhesion method). Because the organic layer is formed by using a transfer material in an aspect of the invention, even if there exist defects and the like (physical defects such as defects in surface smoothness) in the substrate and the organic layer, the influence from the defects can be reduced, and sheet luminescence can be improved. Furthermore, when the adhesion method is used, an organic EL element with fewer defects and excellent durability can be obtained in which layers are tightly bonded.
According to the invention, a composition for an organic electroluminescent element excellent in storability can be provided.
Further, a method for manufacturing an organic electroluminescent element can be provided which can stably and easily manufacture an organic electroluminescent element having high luminous efficiency, high luminance, and excellent durability.
Furthermore, an organic electroluminescent element can be provided which has high luminous efficiency, high luminance, and excellent durability.
All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard is specifically and individually indicated to be incorporated by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-267556 | Sep 2005 | JP | national |
| 2005-267557 | Sep 2005 | JP | national |
| 2006-047240 | Feb 2006 | JP | national |
