Patent Application
20230127629
The present invention relates to an organic electroluminescent device, and an electronic device including the organic electroluminescent device.
In general, an organic electroluminescent device (which may be hereinafter referred to as an “organic EL device”) is constituted by an anode, a cathode, and an organic layer intervening between the anode and the cathode. In application of a voltage between both the electrodes, electrons from the cathode side and holes from the anode side are injected into a light emitting region, and the injected electrons and holes are recombined in the light emitting region to generate an excited state, which then returns to a ground state to emit light. Accordingly, finding a combination of materials that efficiently transport electrons or holes into the light emitting region, promote recombination of the electrons and holes, and efficiently emit excitons is important for obtaining a high-performance organic EL device.
PTLs 1 to 9 describe compounds used as materials for organic EL devices and organic EL devices containing the compounds.
Conventionally, various compounds for organic EL devices have been reported. However, it has been still demanded to further enhance the performance of an organic EL device.
The present invention has been made for solving the aforementioned problem, and an object thereof is to provide an organic EL device which has further improved device performance by containing a combination of specific compounds, and an electronic device which includes the organic EL device.
As a result of the continued investigations by the present inventors on the performance of organic EL devices containing the compounds described in PTLs 1 to 9, it has been found that an organic EL device having a hole blocking layer containing a compound A described below and a light emitting layer containing a host material B described below exhibits higher performance.
In one embodiment, the present invention provides the following organic electroluminescent device.
The organic electroluminescent device has a cathode, an anode, and organic layers intervening between the cathode and the anode, the organic layers including a light emitting layer and an electron transporting layer, the electron transporting layer containing a compound A represented by formula (1), and the light emitting layer containing a host material B represented by formula (10),
wherein
one of Y1 and Y2 is a nitrogen atom and the other one is CR,
R is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 2 to 50 ring carbon atoms, a fluorine atom, and a cyano group;
Ar1 and Ar2 each are independently selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L1 and L2 each are independently a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms;
R1 to R6 each are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group,
adjacent two selected from R1 to R6 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
Cz is represented by the following formula (1-a) or formula (1A):
wherein
R21 to R28 and R31 to R38 each are independently a hydrogen atom or a substituent, and the substituent is selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group;
adjacent two selected from R21 to R28 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
adjacent two selected from R31 to R38 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
R21 and R25, and R34 and R35 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
Ra is selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms;
one selected from R21 to R28 is a single bond bonded to L3 via *a;
*b represents a position bonded to L2;
n is an integer of 1 to 3, and when n is an integer of 2 or 3, Cz's, which are 2 or 3, are the same or different from each other;
L3 and L4 each are independently a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; provided that when n is 2 or 3. L4 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms;
wherein
at least one selected from R101 to R110 each independently is a group represented by formula (31);
when there are two or more groups represented by the formula (31), the two or more groups represented by the formula (31) may be the same or different;
one or more sets of adjacent two selected from R101 to R110 that are not groups represented by the formula (31) may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
R101 to R110, which are not groups represented by the formula (31) and do not form the ring, each independently are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms: —Si(R901)(R902)(R903), —O—(R904), —S—(R905), —N(R906)(R907), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
R901 to R907 each independently is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
when two or more R901 to R907 are present, the two or more R901 to R907 may be the same or different,
-L101-Ar101 (31)
wherein
L101 is a single bond, a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms;
Ar101 is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In another embodiment, the present invention provides an electronic device including the organic electroluminescent device.
An organic EL device having a hole blocking layer containing the compound A and a light emitting layer containing the host material B shows high device performance.
In the description herein, the hydrogen atom encompasses isotopes thereof having different numbers of neutrons, i.e., a light hydrogen atom (protium), a heavy hydrogen atom (deuterium), and tritium.
In the description herein, the bonding site where the symbol, such as “R”, or “D” representing a deuterium atom is not shown is assumed to have a hydrogen atom, i.e., a protium atom, a deuterium atom, or a tritium atom, bonded thereto.
In the description herein, the number of ring carbon atoms shows the number of carbon atoms among the atoms constituting the ring itself of a compound having a structure including atoms bonded to form a ring (such as a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound). In the case where the ring is substituted by a substituent, the carbon atom contained in the substituent is not included in the number of ring carbon atoms. The same definition is applied to the “number of ring carbon atoms” described hereinafter unless otherwise indicated. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridine ring has 5 ring carbon atoms, and a furan ring has 4 ring carbon atoms. For example, 9,9-diphenylfluorenyl group has 13 ring carbon atoms, and 9,9′-spirobifluorenyl group has 25 ring carbon atoms.
In the case where a benzene ring has, for example, an alkyl group substituted thereon as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring carbon atoms of the benzene ring. Accordingly, a benzene ring having an alkyl group substituted thereon has 6 ring carbon atoms. In the case where a naphthalene ring has, for example, an alkyl group substituted thereon as a substituent, the number of carbon atoms of the alkyl group is not included in the number of ring carbon atoms of the naphthalene ring. Accordingly, a naphthalene ring having an alkyl group substituted thereon has 10 ring carbon atoms.
In the description herein, the number of ring atoms shows the number of atoms constituting the ring itself of a compound having a structure including atoms bonded to form a ring (such as a monocyclic ring, a condensed ring, and a set of rings) (such as a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, and a heterocyclic compound). The atom that does not constitute the ring (such as a hydrogen atom terminating the bond of the atom constituting the ring) and, in the case where the ring is substituted by a substituent, the atom contained in the substituent are not included in the number of ring atoms. The same definition is applied to the “number of ring atoms” described hereinafter unless otherwise indicated. For example, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. For example, the number of hydrogen atoms bonded to a pyridine ring or atoms constituting a substituent is not included in the number of ring atoms of the pyridine ring. Accordingly, a pyridine ring having a hydrogen atom or a substituent bonded thereto has 6 ring atoms. For example, the number of hydrogen atoms bonded to carbon atoms of a quinazoline ring or atoms constituting a substituent is not included in the number of ring atoms of the quinazoline ring. Accordingly, a quinazoline ring having a hydrogen atom or a substituent bonded thereto has 10 ring atoms.
In the description herein, the expression “having XX to YY carbon atoms” in the expression “substituted or unsubstituted ZZ group having XX to YY carbon atoms” means the number of carbon atoms of the unsubstituted ZZ group, and, in the case where the ZZ group is substituted, the number of carbon atoms of the substituent is not included. Herein, “YY” is larger than “XX”, “XX” represents an integer of 1 or more, and “YY” represents an integer of 2 or more.
In the description herein, the expression “having XX to YY atoms” in the expression “substituted or unsubstituted ZZ group having XX to YY atoms” means the number of atoms of the unsubstituted ZZ group, and, in the case where the ZZ group is substituted, the number of atoms of the substituent is not included. Herein, “YY” is larger than “XX”, “XX” represents an integer of 1 or more, and “YY” represents an integer of 2 or more.
In the description herein, an unsubstituted ZZ group means the case where the “substituted or unsubstituted ZZ group” is an “unsubstituted ZZ group”, and a substituted ZZ group means the case where the “substituted or unsubstituted ZZ group” is a “substituted ZZ group”.
In the description herein, the expression “unsubstituted” in the expression “substituted or unsubstituted ZZ group” means that hydrogen atoms in the ZZ group are not substituted by a substituent. The hydrogen atoms in the “unsubstituted ZZ group” each are a protium atom, a deuterium atom, or a tritium atom.
In the description herein, the expression “substituted” in the expression “substituted or unsubstituted ZZ group” means that one or more hydrogen atom in the ZZ group is substituted by a substituent. The expression “substituted” in the expression “BB group substituted by an AA group” similarly means that one or more hydrogen atom in the BB group is substituted by the AA group.
The substituents described in the description herein will be explained.
In the description herein, the number of ring carbon atoms of the “unsubstituted aryl group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, the number of ring atoms of the “unsubstituted heterocyclic group” is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkyl group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkenyl group” is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkynyl group” is 2 to 50, preferably 2 to 20, and more preferably 2 to 6, unless otherwise indicated in the description.
In the description herein, the number of ring carbon atoms of the “unsubstituted cycloalkyl group” is 3 to 50, preferably 3 to 20, and more preferably 3 to 6, unless otherwise indicated in the description.
In the description herein, the number of ring carbon atoms of the “unsubstituted arylene group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, the number of ring atoms of the “unsubstituted divalent heterocyclic group” is 5 to 50, preferably 5 to 30, and more preferably 5 to 18, unless otherwise indicated in the description.
In the description herein, the number of carbon atoms of the “unsubstituted alkylene group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, specific examples (set of specific examples G1) of the “substituted or unsubstituted aryl group” include the unsubstituted aryl groups (set of specific examples G1A) and the substituted aryl groups (set of specific examples G1B) shown below. (Herein, the unsubstituted aryl group means the case where the “substituted or unsubstituted aryl group” is an “unsubstituted aryl group”, and the substituted aryl group means the case where the “substituted or unsubstituted aryl group” is a “substituted aryl group”.) In the description herein, the simple expression “aryl group” encompasses both the “unsubstituted aryl group” and the “substituted aryl group”.
The “substituted aryl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted aryl group” by a substituent. Examples of the “substituted aryl group” include groups formed by one or more hydrogen atom of each of the “unsubstituted aryl groups” in the set of specific examples G1A by a substituent, and the examples of the substituted aryl groups in the set of specific examples G1B. The examples of the “unsubstituted aryl group” and the examples of the “substituted aryl group” enumerated herein are mere examples, and the “substituted aryl group” in the description herein encompasses groups formed by substituting a hydrogen atom bonded to the carbon atom of the aryl group itself of each of the “substituted aryl groups” in the set of specific examples G1B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted aryl groups” in the set of specific examples G1B by a substituent.
a phenyl group,
a p-biphenyl group,
a m-biphenyl group,
an o-biphenyl group,
a p-terphenyl-4-yl group,
a p-terphenyl-3-yl group,
a p-terphenyl-2-yl group,
a m-terphenyl-4-yl group,
a m-terphenyl-3-yl group,
a m-terphenyl-2-yl group,
an o-terphenyl-4-yl group,
an o-terphenyl-3-yl group,
an o-terphenyl-2-yl group,
a 1-naphthyl group,
a 2-naphthyl group,
an anthryl group,
a benzanthryl group,
a phenanthryl group,
a benzophenanthryl group,
a phenarenyl group,
a pyrenyl group,
a chrysenyl group,
a benzochrysenyl group,
a triphenylenyl group,
a benzotriphenylenyl group,
a tetracenyl group,
a pentacenyl group,
a fluorenyl group,
a 9,9′-spirobifluorenyl group,
a benzofluorenyl group,
a dibenzofluorenyl group,
a fluoranthenyl group,
a benzofluoranthenyl group,
a perylenyl group, and
monovalent aryl groups derived by removing one hydrogen atom from each of the ring structures represented by the following general formulae (TEMP-1) to (TEMP-15):
an o-tolyl group,
a m-tolyl group,
a p-tolyl group,
a p-xylyl group,
a m-xylyl group,
an o-xylyl group,
a p-isopropylphenyl group,
a m-isopropylphenyl group,
an o-isopropylphenyl group,
a p-t-butylphenyl group,
a m-t-butylphenyl group,
a o-t-butylphenyl group,
a 3,4,5-trimethylphenyl group,
a 9,9-dimethylfluorenyl group,
a 9,9-diphenylfluorenyl group,
a 9,9-bis(4-methylphenyl)fluorenyl group,
a 9,9-bis(4-isopropylphenyl)fluorenyl group,
a 9,9-bis(4-t-butylphenyl)fluorenyl group,
a cyanophenyl group,
a triphenylsilylphenyl group,
a trimethylsilylphenyl group,
a phenylnaphthyl group,
a naphthylphenyl group, and
groups formed by substituting one or more hydrogen atom of each of monovalent aryl groups derived from the ring structures represented by the general formulae (TEMP-1) to (TEMP-15) by a substituent.
In the description herein, the “heterocyclic group” means a cyclic group containing at least one hetero atom in the ring atoms. Specific examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.
In the description herein, the “heterocyclic group” is a monocyclic group or a condensed ring group.
In the description herein, the “heterocyclic group” is an aromatic heterocyclic group or a non-aromatic heterocyclic group.
In the description herein, specific examples (set of specific examples G2) of the “substituted or unsubstituted heterocyclic group” include the unsubstituted heterocyclic groups (set of specific examples G2A) and the substituted heterocyclic groups (set of specific examples G2B) shown below. (Herein, the unsubstituted heterocyclic group means the case where the “substituted or unsubstituted heterocyclic group” is an “unsubstituted heterocyclic group”, and the substituted heterocyclic group means the case where the “substituted or unsubstituted heterocyclic group” is a “substituted heterocyclic group”.) In the description herein, the simple expression “heterocyclic group” encompasses both the “unsubstituted heterocyclic group” and the “substituted heterocyclic group”.
The “substituted heterocyclic group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted heterocyclic group” by a substituent. Specific examples of the “substituted heterocyclic group” include groups formed by substituting a hydrogen atom of each of the “unsubstituted heterocyclic groups” in the set of specific examples G2A by a substituent, and the examples of the substituted heterocyclic groups in the set of specific examples G2B. The examples of the “unsubstituted heterocyclic group” and the examples of the “substituted heterocyclic group” enumerated herein are mere examples, and the “substituted heterocyclic group” in the description herein encompasses groups formed by substituting a hydrogen atom bonded to the ring atom of the heterocyclic group itself of each of the “substituted heterocyclic groups” in the set of specific examples G2B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted heterocyclic groups” in the set of specific examples G2B by a substituent.
The set of specific examples G2A includes, for example, the unsubstituted heterocyclic group containing a nitrogen atom (set of specific examples G2A1), the unsubstituted heterocyclic group containing an oxygen atom (set of specific examples G2A2), the unsubstituted heterocyclic group containing a sulfur atom (set of specific examples G2A3), and monovalent heterocyclic groups derived by removing one hydrogen atom from each of the ring structures represented by the following general formulae (TEMP-16) to (TEMP-33) (set of specific examples G2A4).
The set of specific examples G2B includes, for example, the substituted heterocyclic groups containing a nitrogen atom (set of specific examples G2B1), the substituted heterocyclic groups containing an oxygen atom (set of specific examples G2B2), the substituted heterocyclic groups containing a sulfur atom (set of specific examples G2B3), and groups formed by substituting one or more hydrogen atom of each of monovalent heterocyclic groups derived from the ring structures represented by the following general formulae (TEMP-16) to (TEMP-33) by a substituent (set of specific examples G2B4).
Unsubstituted Heterocyclic Group containing Nitrogen Atom (Set of Specific Examples G2A1):
a pyrrolyl group,
an imidazolyl group,
a pyrazolyl group,
a triazolyl group,
a tetrazolyl group,
an oxazolyl group,
an isoxazolyl group,
an oxadiazolyl group,
a thiazolyl group,
an isothiazolyl group,
a thiadiazolyl group,
a pyridyl group,
a pyridazinyl group,
a pyrimidinyl group,
a pyrazinyl group,
a triazinyl group,
an indolyl group,
an isoindolyl group,
an indolizinyl group,
a quinolizinyl group,
a quinolyl group,
an isoquinolyl group,
a cinnolinyl group,
a phthalazinyl group,
a quinazolinyl group,
a quinoxalinyl group,
a benzimidazolyl group,
an indazolyl group,
a phenanthrolinyl group,
a phenanthridinyl group,
an acridinyl group,
a phenazinyl group,
a carbazolyl group,
a benzocarbazolyl group,
a morpholino group,
a phenoxazinyl group,
a phenothiazinyl group,
an azacarbazolyl group, and
a diazacarbazolyl group.
Unsubstituted Heterocyclic Group containing Oxygen Atom (Set of Specific Examples G2A2):
a furyl group,
an oxazolyl group,
an isoxazolyl group,
an oxadiazolyl group,
a xanthenyl group,
a benzofuranyl group,
an isobenzofuranyl group,
a dibenzofuranyl group,
a naphthobenzofuranyl group,
a benzoxazolyl group,
a benzisoxazolyl group,
a phenoxazinyl group,
a morpholino group,
a dinaphthofuranyl group,
an azadibenzofuranyl group,
a diazadibenzofuranyl group,
an azanaphthobenzofuranyl group, and
a diazanaphthobenzofuranyl group.
Unsubstituted Heterocyclic Group containing Sulfur Atom (Set of Specific Examples G2A3):
a thienyl group,
a thiazolyl group,
an isothiazolyl group,
a thiadiazolyl group,
a benzothiophenyl group (benzothienyl group),
an isobenzothiophenyl group (isobenzothienyl group),
a dibenzothiophenyl group (dibenzothienyl group),
a naphthobenzothiophenyl group (naphthobenzothienyl group),
a benzothiazolyl group,
a benzisothiazolyl group,
a phenothiazinyl group,
a dinaphthothiophenyl group (dinaphthothienyl group),
an azadibenzothiophenyl group (azadibenzothienyl group),
a diazadibenzothiophenyl group (diazadibenzothienyl group),
an azanaphthobenzothiophenyl group (azanaphthobenzothienyl group), and
a diazanaphthobenzothiophenyl group (diazanaphthobenzothienyl group).
Monovalent Heterocyclic Group Derived by Removing One Hydrogen Atom from Ring Structures Represented by General Formulae (TEMP-16) to (TEMP-33) (Set of Specific Examples G2A4)
In the general formulae (TEMP-16) to (TEMP-33), XA and YA each independently, represent an oxygen atom, a sulfur atom, NH, or CH2, provided that at least one of XA and YA represents an oxygen atom, a sulfur atom, or NB.
In the general formulae (TEMP-16) to (TEMP-33): in the case where at least one of XA and YA, represents NH or CH2, the monovalent heterocyclic groups derived from the ring structures represented by the general formulae (TEMP-16) to (TEMP-33) include monovalent groups formed by removing one hydrogen atom from the NH or CH2.
Substituted Heterocyclic Group containing Nitrogen Atom (Set of Specific Examples G2B1):
a (9-phenyl)carbazolyl group,
a (9-biphenyl)carbazolyl group,
a (9-phenyl)phenylcarbazolyl group,
a (9-naphthyl)carbazolyl group,
a diphenylcarbazol-9-yl group,
a phenylcarbazol-9-yl group,
a methylbenzimidazolyl group,
an ethylbenzimidazolyl group,
a phenyltriazinyl group,
a biphenyltriazinyl group,
a diphenyltriazinyl group,
a phenylquinazolinyl group, and
a biphenylquinazolinyl group.
a phenyldibenzofuranyl group,
a methyldibenzofuranyl group,
a t-butyldibenzofuranyl group, and
a monovalent residual group of spiro[9H-xanthene-9,9′-[9H]fluorene].
a phenyldibenzothiophenyl group,
a methyldibenzothiophenyl group,
a t-butyldibenzothiophenyl group, and
a monovalent residual group of spiro[9H-thioxanthene-9,9′-[9H]fluorene].
Group Formed by Substituting One or More Hydrogen Atom of Monovalent Heterocyclic Group Derived from Ring Structures Represented by General Formulae (TEMP-16) to (TEMP-33) by Substituent (Set of Specific Examples G2B4)
The “one or more hydrogen atom of the monovalent heterocyclic group” means one or more hydrogen atom selected from the hydrogen atom bonded to the ring carbon atom of the monovalent heterocyclic group, the hydrogen atom bonded to the nitrogen atom in the case where at least one of XA and YA represents NH, and the hydrogen atom of the methylene group in the case where one of XA and YA represents CH2.
In the description herein, specific examples (set of specific examples G3) of the “substituted or unsubstituted alkyl group” include the unsubstituted alkyl groups (set of specific examples G3A) and the substituted alkyl groups (set of specific examples G3B) shown below. (Herein, the unsubstituted alkyl group means the case where the “substituted or unsubstituted alkyl group” is an “unsubstituted alkyl group”, and the substituted alkyl group means the case where the “substituted or unsubstituted alkyl group” is a “substituted alkyl group”.) In the description herein, the simple expression “alkyl group” encompasses both the “unsubstituted alkyl group” and the “substituted alkyl group”.
The “substituted alkyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkyl group” by a substituent. Specific examples of the “substituted alkyl group” include groups formed by substituting one or more hydrogen atom of each of the “unsubstituted alkyl groups” (set of specific examples G3A) by a substituent, and the examples of the substituted alkyl groups (set of specific examples G3B). In the description herein, the alkyl group in the “unsubstituted alkyl group” means a chain-like alkyl group. Accordingly, the “unsubstituted alkyl group” encompasses an “unsubstituted linear alkyl group” and an “unsubstituted branched alkyl group”. The examples of the “unsubstituted alkyl group” and the examples of the “substituted alkyl group” enumerated herein are mere examples, and the “substituted alkyl group” in the description herein encompasses groups formed by substituting a hydrogen atom of the alkyl group itself of each of the “substituted alkyl groups” in the set of specific examples G3B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted alkyl groups” in the set of specific examples G3B by a substituent.
a methyl group,
an ethyl group,
a n-propyl group,
an isopropyl group,
a n-butyl group,
an isobutyl group,
a s-butyl group, and
a t-butyl group.
a heptafluoropropyl group (including isomers),
a pentafluoroethyl group,
a 2,2,2-trifluoroethyl group, and
a trifluoromethyl group.
In the description herein, specific examples (set of specific examples G4) of the “substituted or unsubstituted alkenyl group” include the unsubstituted alkenyl groups (set of specific examples G4A) and the substituted alkenyl groups (set of specific examples G4B) shown below. (Herein, the unsubstituted alkenyl group means the case where the “substituted or unsubstituted alkenyl group” is an “unsubstituted alkenyl group”, and the substituted alkenyl group means the case where the “substituted or unsubstituted alkenyl group” is a “substituted alkenyl group”.) In the description herein, the simple expression “alkenyl group” encompasses both the “unsubstituted alkenyl group” and the “substituted alkenyl group”.
The “substituted alkenyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkenyl group” by a substituent. Specific examples of the “substituted alkenyl group” include the “unsubstituted alkenyl groups” (set of specific examples G4A) that each have a substituent, and the examples of the substituted alkenyl groups (set of specific examples G4B). The examples of the “unsubstituted alkenyl group” and the examples of the “substituted alkenyl group” enumerated herein are mere examples, and the “substituted alkenyl group” in the description herein encompasses groups formed by substituting a hydrogen atom of the alkenyl group itself of each of the “substituted alkenyl groups” in the set of specific examples G4B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of each of the “substituted alkenyl groups” in the set of specific examples G4B by a substituent.
a vinyl group,
an allyl group,
a 1-butenyl group,
a 2-butenyl group, and
a 3-butenyl group.
a 1,3-butanedienyl group,
a 1-methylvinyl group,
a 1-methylallyl group,
a 1,1-dimethylallyl group,
a 2-methylallyl group, and
a 1,2-dimethylallyl group.
In the description herein, specific examples (set of specific examples G5) of the “substituted or unsubstituted alkynyl group” include the unsubstituted alkynyl group (set of specific examples G5A) shown below. (Herein, the unsubstituted alkynyl group means the case where the “substituted or unsubstituted alkynyl group” is an “unsubstituted alkynyl group”.) In the description herein, the simple expression “alkynyl group” encompasses both the “unsubstituted alkynyl group” and the “substituted alkynyl group”.
The “substituted alkynyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted alkynyl group” by a substituent. Specific examples of the “substituted alkenyl group” include groups formed by substituting one or more hydrogen atom of the “unsubstituted alkynyl group” (set of specific examples G5A) by a substituent.
an ethynyl group.
In the description herein, specific examples (set of specific examples G6) of the “substituted or unsubstituted cycloalkyl group” include the unsubstituted cycloalkyl groups (set of specific examples G6A) and the substituted cycloalkyl group (set of specific examples G6B) shown below. (Herein, the unsubstituted cycloalkyl group means the case where the “substituted or unsubstituted cycloalkyl group” is an “unsubstituted cycloalkyl group”, and the substituted cycloalkyl group means the case where the “substituted or unsubstituted cycloalkyl group” is a “substituted cycloalkyl group”.) In the description herein, the simple expression “cycloalkyl group” encompasses both the “unsubstituted cycloalkyl group” and the “substituted cycloalkyl group”.
The “substituted cycloalkyl group” means a group formed by substituting one or more hydrogen atom of the “unsubstituted cycloalkyl group” by a substituent. Specific examples of the “substituted cycloalkyl group” include groups formed by substituting one or more hydrogen atom of each of the “unsubstituted cycloalkyl groups” (set of specific examples G6A) by a substituent, and the example of the substituted cycloalkyl group (set of specific examples G6B). The examples of the “unsubstituted cycloalkyl group” and the examples of the “substituted cycloalkyl group” enumerated herein are mere examples, and the “substituted cycloalkyl group” in the description herein encompasses groups formed by substituting one or more hydrogen atom bonded to the carbon atoms of the cycloalkyl group itself of the “substituted cycloalkyl group” in the set of specific examples G6B by a substituent, and groups formed by substituting a hydrogen atom of the substituent of the “substituted cycloalkyl group” in the set of specific examples G6B by a substituent.
a cyclopropyl group,
a cyclobutyl group,
a cyclopentyl group,
a cyclohexyl group,
a 1-adamantyl group,
a 2-adamantyl group,
a 1-norbornyl group, and
a 2-norbornyl group.
a 4-methylcyclohexyl group.
Group represented by —Si(R901)(R902)(R903)
In the description herein, specific examples (set of specific examples G7) of the group represented by —Si(R901)(R902)(R903) include:
—Si(G1)(G1)(G1),
—Si(G1)(G2)(G2),
—Si(G1)(G1)(G2),
—Si(G2)(G2)(G2),
—Si(G3)(G3)(G3), and
—Si(G6)(G6)(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
Plural groups represented by G1 in —Si(G1)(G1)(G1) are the same as or different from each other.
Plural groups represented by G2 in —Si(G1)(G2)(G2) are the same as or different from each other.
Plural groups represented by G1 in —Si(G1)(G1)(G2) are the same as or different from each other.
Plural groups represented by G2 in —Si(G2)(G2)(G2) are the same as or different from each other.
Plural groups represented by G3 in −Si(G3)(G3)(G3) are the same as or different from each other.
Plural groups represented by G6 in −Si(G6)(G6)(G6) are the same as or different from each other.
Group represented by —O—(R904)
In the description herein, specific examples (set of specific examples G8) of the group represented by —O—(R904) include:
—O(G1),
—O(G2),
—O(G3), and
—O(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
In the description herein, specific examples (set of specific examples G9) of the group represented by —S—(R905) include:
—S(G1),
—S(G2),
—S(G3), and
—S(G6).
Herein,
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
Group Represented by —N(R906)(R907)
In the description herein, specific examples (set of specific examples G10) of the group represented by —N(R906)(R907) include:
—N(G1)(G1),
—N(G2)(G2),
—N(G1)(G2),
—N(G3)(G3), and
—N(G6)(G6).
G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1,
G2 represents the “substituted or unsubstituted heterocyclic group” described in the set of specific examples G2,
G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and
G6 represents the “substituted or unsubstituted cycloalkyl group” described in the set of specific examples G6.
Plural groups represented by G1 in —N(G1)(G1) are the same as or different from each other.
Plural groups represented by G2 in —N(G2)(G2) are the same as or different from each other.
Plural groups represented by G3 in —N(G3)(G3) are the same as or different from each other.
Plural groups represented by G6 in —N(G6)(G6) are the same as or different from each other.
In the description herein, specific examples (set of specific examples G11) of the “halogen atom” include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the description herein, the “substituted or unsubstituted fluoroalkyl group” means a group formed by substituting at least one hydrogen atom bonded to the carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” by a fluorine atom, and encompasses a group formed by substituting all the hydrogen atoms bonded to the carbon atoms constituting the alkyl group in the “substituted or unsubstituted alkyl group” by fluorine atoms (i.e., a perfluoroalkyl group). The number of carbon atoms of the “unsubstituted fluoroalkyl group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description. The “substituted fluoroalkyl group” means a group formed by substituting one or more hydrogen atom of the “fluoroalkyl group” by a substituent. In the description herein, the “substituted fluoroalkyl group” encompasses a group formed by substituting one or more hydrogen atom bonded to the carbon atom of the alkyl chain in the “substituted fluoroalkyl group” by a substituent, and a group formed by substituting one or more hydrogen atom of the substituent in the “substituted fluoroalkyl group” by a substituent. Specific examples of the “unsubstituted fluoroalkyl group” include examples of groups formed by substituting one or more hydrogen atom in each of the “alkyl group” (set of specific examples G3) by a fluorine atom.
In the description herein, the “substituted or unsubstituted haloalkyl group” means a group formed by substituting at least one hydrogen atom bonded to the carbon atom constituting the alkyl group in the “substituted or unsubstituted alkyl group” by a halogen atom, and encompasses a group formed by substituting all the hydrogen atoms bonded to the carbon atoms constituting the alkyl group in the “substituted or unsubstituted alkyl group” by halogen atoms. The number of carbon atoms of the “unsubstituted haloalkyl group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description. The “substituted haloalkyl group” means a group formed by substituting one or more hydrogen atom of the “haloalkyl group” by a substituent. In the description herein, the “substituted haloalkyl group” encompasses a group formed by substituting one or more hydrogen atom bonded to the carbon atom of the alkyl chain in the “substituted haloalkyl group” by a substituent, and a group formed by substituting one or more hydrogen atom of the substituent in the “substituted haloalkyl group” by a substituent. Specific examples of the “unsubstituted haloalkyl group” include examples of groups formed by substituting one or more hydrogen atom in each of the “alkyl group” (set of specific examples G3) by a halogen atom. A haloalkyl group may be referred to as a halogenated alkyl group in some cases.
In the description herein, specific examples of the “substituted or unsubstituted alkoxy group” include a group represented by —O(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. The number of carbon atoms of the “unsubstituted alkoxy group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted alkylthio group” include a group represented by —S(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. The number of carbon atoms of the “unsubstituted alkylthio group” is 1 to 50, preferably 1 to 30, and more preferably 1 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted aryloxy group” include a group represented by —O(G1), wherein G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. The number of ring carbon atoms of the “unsubstituted aryloxy group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted arylthio group” include a group represented by —S(G1), wherein G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. The number of ring carbon atoms of the “unsubstituted arylthio group” is 6 to 50, preferably 6 to 30, and more preferably 6 to 18, unless otherwise indicated in the description.
In the description herein, specific examples of the “trialkylsilyl group” include a group represented by —Si(G3)(G3)(G3), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3. Plural groups represented by G3 in —Si(G3)(G3)(G3) are the same as or different from each other. The number of carbon atoms of each of alkyl groups of the “substituted or unsubstituted trialkylsilyl group” is 1 to 50, preferably 1 to 20, and more preferably 1 to 6, unless otherwise indicated in the description.
In the description herein, specific examples of the “substituted or unsubstituted aralkyl group” include a group represented by -(G3)-(G1), wherein G3 represents the “substituted or unsubstituted alkyl group” described in the set of specific examples G3, and G1 represents the “substituted or unsubstituted aryl group” described in the set of specific examples G1. Accordingly, the “aralkyl group” is a group formed by substituting a hydrogen atom of an “alkyl group” by an “aryl group” as a substituent, and is one embodiment of the “substituted alkyl group”. The “unsubstituted aralkyl group” is an “unsubstituted alkyl group” that is substituted by an “unsubstituted aryl group”, and the number of carbon atoms of the “unsubstituted aralkyl group” is 7 to 50, preferably 7 to 30, and more preferably 7 to 18, unless otherwise indicated in the description.
Specific examples of the “substituted or unsubstituted aralkyl group” include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 1-phenylisopropyl group, a 2-phenylisopropyl group, a phenyl-t-butyl group, an α-naphthylmethyl group, a 1-α-naphthylethyl group, a 2-α-naphthylethyl group, a 1-α-naphthylisopropyl group, a 2-α-naphthylisopropyl group, a 6-naphthylmethyl group, a 1-β-naphthylethyl group, a 2-β-naphthylethyl group, a 1-β-naphthylisopropyl group, and a 2-β-naphthylisopropyl group.
In the description herein, the substituted or unsubstituted aryl group is preferably a phenyl group, a p-biphenyl group, a m-biphenyl group, an o-biphenyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl-4-yl group, a m-terphenyl-3-yl group, a m-terphenyl-2-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group, an o-terphenyl-2-yl group, a 1-naphthyl group, a 2-naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a triphenylenyl group, a fluorenyl group, a 9,9′-spirobifluorenyl group, a 9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, and the like, unless otherwise indicated in the description.
In the description herein, the substituted or unsubstituted heterocyclic group is preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a benzimidazolyl group, a phenanthrolinyl group, a carbazolyl group (e.g., a 1-carbazolyl, group, a 2-carbazolyl, group, a 3-carbazolyl, group, a 4-carbazolyl, group, or a 9-carbazolyl, group), a benzocarbazolyl group, an azacarbazolyl group, a diazacarbazolyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, an azadibenzofuranyl group, a diazadibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzothiophenyl group, an azadibenzothiophenyl group, a diazadibenzothiophenyl group, a (9-phenylcarbazolyl group (e.g., a (9-phenypearbazol-1-yl group, a (9-phenyl)carbazol-2-yl group, a (9-phenyl)carbazol-3-yl group, or a (9-phenyl)carbazol-4-yl group), a (9-biphenylyl)carbazolyl group, a (9-phenyl)phenyl)carbazolyl group, a diphenylcarbazol-9-yl group, a phenylcarbazol-9-yl group, a phenyltriazinyl group, a biphenylyltriazinyl group, a dipbenyltriazinyl group, a phenyldibenzofuranyl group, a phenyldibenzothiophenyl group, and the like, unless otherwise indicated in the description.
In the description herein, the carbazolyl group is specifically any one of the following groups unless otherwise indicated in the description.
In the description herein, the (9-phenyl)carbazolyl group is specifically any one of the following groups unless otherwise indicated in the description.
In the general formulae (TEMP-Cz1) to (TEMP-Cz9), * represents a bonding site.
In the description herein, the dibenzofuranyl group and the dibenzothiophenyl group are specifically any one of the following groups unless otherwise indicated in the description.
In the general formulae (TEMP-34) to (TEMP-41), * represents a bonding site.
In the description herein, the substituted or unsubstituted alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, or the like unless otherwise indicated in the description.
In the description herein, the “substituted or unsubstituted arylene group” is a divalent group derived by removing one hydrogen atom on the aryl ring from the “substituted or unsubstituted aryl group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G12) of the “substituted or unsubstituted arylene group” include divalent groups derived by removing one hydrogen atom on the aryl ring from the “substituted or unsubstituted aryl groups” described in the set of specific examples G1.
In the description herein, the “substituted or unsubstituted divalent heterocyclic group” is a divalent group derived by removing one hydrogen atom on the heterocyclic ring from the “substituted or unsubstituted heterocyclic group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G13) of the “substituted or unsubstituted divalent heterocyclic group” include divalent groups derived by removing one hydrogen atom on the heterocyclic ring from the “substituted or unsubstituted heterocyclic groups” described in the set of specific examples G2.
In the description herein, the “substituted or unsubstituted alkylene group” is a divalent group derived by removing one hydrogen atom on the alkyl chain from the “substituted or unsubstituted alkyl group” described above unless otherwise indicated in the description. Specific examples (set of specific examples G14) of the “substituted or unsubstituted alkylene group” include divalent groups derived by removing one hydrogen atom on the alkyl chain from the “substituted or unsubstituted alkyl groups” described in the set of specific examples G3.
In the description herein, the substituted or unsubstituted arylene group is preferably any one of the groups represented by the following general formulae (TEMP-42) to (TEMP-68) unless otherwise indicated in the description.
in the general formulae (TEMP-42) to (TEMP-52), Q1 to Q10 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-42) to (TEMP-52), * represents a bonding site.
In the general formulae (TEMP-53) to (TEMP-62), Q1 to Q10 each independently represent a hydrogen atom or a substituent.
The formulae Q9 and Q10 may be bonded to each other to form a ring via a single bond,
In the general formulae (TEMP-53) to (TEMP-62), * represents a bonding site.
In the general formulae (TEMP-63) to (TEMP-68), Q1 to Q8 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-63) to (TEMP-68), * represents a bonding site.
In the description herein, the substituted or unsubstituted divalent heterocyclic group is preferably the groups represented by the following general formulae (TEMP-69) to (TEMP-102) unless otherwise indicated in the description.
In the general formulae (TEMP-69) to (TEMP-82), Q1 to Q9 each independently represent a hydrogen atom or a substituent.
In the general formulae (TEMP-69) to (TEMP-102), Q1 to Q9 each independently represent a hydrogen atom or a substituent.
The above are the explanation of the “substituents in the description herein”.
In the description herein, the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring, or each are bonded to each other to form a substituted or unsubstituted condensed ring, or each are not bonded to each other” means a case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring”, a case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted condensed ring”, and a case where “one or more combinations of combinations each including adjacent two or more each are not bonded to each other”.
In the description herein, the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted monocyclic ring” and the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted condensed ring” (which may be hereinafter collectively referred to as a “case forming a ring by bonding”) will be explained below. The cases will be explained for the anthracene compound represented by the following general formula (TEMP-103) having an anthracene core skeleton as an example.
For example, in the case where “one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a ring” among R921 to R930, the combinations each including adjacent two as one combination include a combination of R921 and R922, a combination of R922 and R923, a combination of R923 and R924, a combination of R924 and R930, a combination of R930 and R925, a combination of R925 and R926, a combination of R926 and R927, a combination of R927 and R928, a combination of R928 and R929, and a combination of R929 and R921.
The “one or more combinations” mean that two or more combinations each including adjacent two or more may form rings simultaneously. For example, in the case where R921 and R922 are bonded to each other to form a ring QA, and simultaneously R925 and R926 are bonded to each other to form a ring QB, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-104).
The case where the “combination including adjacent two or more forms rings” encompasses not only the case where adjacent two included in the combination are bonded as in the aforementioned example, but also the case where adjacent three or more included in the combination are bonded. For example, this case means that R921 and R922 are bonded to each other to form a ring QA, R922 and R923 are bonded to each other to form a ring QC, and adjacent three (R921, R922, and R923) included in the combination are bonded to each other to form rings, which are condensed to the anthracene core skeleton, and in this case, the anthracene compound represented by the general formula (TEMP-103) is represented by the following general formula (TEMP-105). In the following general formula (TEMP-105), the ring QA and the ring QC share R922.
The formed “monocyclic ring” or “condensed ring” may be a saturated ring or an unsaturated ring in terms of structure of the formed ring itself. In the case where the “one combination including adjacent two” forms a “monocyclic ring” or a “condensed ring”, the “monocyclic ring” or the “condensed ring” may form a saturated ring or an unsaturated ring. For example, the ring QA and the ring QB formed in the general formula (TEMP-104) each are a “monocyclic ring” or a “condensed ring”. The ring QA and the ring QC formed in the general formula (TEMP-105) each are a “condensed ring”. The ring QA and the ring QC in the general formula (TEMP-105) form a condensed ring through condensation of the ring QA and the ring QC. In the case where the ring QA in the general formula (TEMP-104) is a benzene ring, the ring QA is a monocyclic ring. In the case where the ring QA in the general formula (TMEP-104) is a naphthalene ring, the ring QA is a condensed ring.
The “unsaturated ring” means an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The “saturated ring” means an aliphatic hydrocarbon ring or a non-aromatic heterocyclic ring.
Specific examples of the aromatic hydrocarbon ring include the structures formed by terminating the groups exemplified as the specific examples in the set of specific examples G1 with a hydrogen atom.
Specific examples of the aromatic heterocyclic ring include the structures formed by terminating the aromatic heterocyclic groups exemplified as the specific examples in the set of specific examples G2 with a hydrogen atom.
Specific examples of the aliphatic hydrocarbon ring include the structures formed by terminating the groups exemplified as the specific examples in the set of specific examples G6 with a hydrogen atom.
The expression “to form a ring” means that the ring is formed only with the plural atoms of the core structure or with the plural atoms of the core structure and one or more arbitrary element. For example, the ring QA formed by bonding R921 and R922 each other shown in the general formula (TEMP-104) means a ring formed with the carbon atom of the anthracene skeleton bonded to R921, the carbon atom of the anthracene skeleton bonded to R922, and one or more arbitrary element. As a specific example, in the case where the ring QA is formed with R921 and R922, and in the case where a monocyclic unsaturated ring is formed with the carbon atom of the anthracene skeleton bonded to R921, the carbon atom of the anthracene skeleton bonded to R922, and four carbon atoms, the ring formed with R921 and R922 is a benzene ring.
Herein, the “arbitrary element” is preferably at least one kind of an element selected from the group consisting of a carbon element, a nitrogen element, an oxygen element, and a sulfur element, unless otherwise indicated in the description. For the arbitrary element (for example, for a carbon element or a nitrogen element), a bond that does not form a ring may be terminated with a hydrogen atom or the like, and may be substituted by an “arbitrary substituent” described later. In the case where an arbitrary element other than a carbon element is contained, the formed ring is a heterocyclic ring.
The number of the “one or more arbitrary element” constituting the monocyclic ring or the condensed ring is preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and further preferably 3 or more and 5 or less, unless otherwise indicated in the description.
What is preferred between the “monocyclic ring” and the “condensed ring” is the “monocyclic ring” unless otherwise indicated in the description.
What is preferred between the “saturated ring” and the “unsaturated ring” is the “unsaturated ring” unless otherwise indicated in the description.
The “monocyclic ring” is preferably a benzene ring unless otherwise indicated in the description.
The “unsaturated ring” is preferably a benzene ring unless otherwise indicated in the description.
In the case where the “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted monocyclic ring”, or each are “bonded to each other to form a substituted or unsubstituted condensed ring”, it is preferred that the one or more combinations of combinations each including adjacent two or more each are bonded to each other to form a substituted or unsubstituted “unsaturated ring” containing the plural atoms of the core skeleton and 1 or more and 15 or less at least one kind of an element selected from the group consisting of a carbon element, a nitrogen element, an oxygen element, and a sulfur element, unless otherwise indicated in the description.
In the case where the “monocyclic ring” or the “condensed ring” has a substituent, the substituent is, for example, an “arbitrary substituent” described later. In the case where the “monocyclic ring” or the “condensed ring” has a substituent, specific examples of the substituent include the substituents explained in the section “Substituents in Description” described above.
In the case where the “saturated ring” or the “unsaturated ring” has a substituent, the substituent is, for example, an “arbitrary substituent” described later. In the case where the “monocyclic ring” or the “condensed ring” has a substituent, specific examples of the substituent include the substituents explained in the section “Substituents in Description” described above.
The above are the explanation of the case where “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted monocyclic ring”, and the case where “one or more combinations of combinations each including adjacent two or more” each are “bonded to each other to form a substituted or unsubstituted condensed ring” (i.e., the “case forming a ring by bonding”).
In one embodiment in the description herein, the substituent for the case of “substituted or unsubstituted” (which may be hereinafter referred to as an “arbitrary substituent”) is, for example, a group selected from the group consisting of
an unsubstituted alkyl group having 1 to 50 carbon atoms,
an unsubstituted alkenyl group having 2 to 50 carbon atoms,
an unsubstituted alkynyl group having 2 to 50 carbon atoms,
an unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms,
—Si(R901) (R902) (R903),
—O—(R904),
—S—(R905),
—N(R906)(R907),
a halogen atom, a cyano group, a nitro group,
an unsubstituted aryl group having 6 to 50 ring carbon atoms, and
an unsubstituted heterocyclic group having 5 to 50 ring atoms,
wherein R901 to R907 each independently represent
a hydrogen atom,
a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms
a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms,
a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
In the case where two or more groups each represented by R901 exist, the two or more groups each represented by R901 are the same as or different from each other,
in the case where two or more groups each represented by R902 exist, the two or more groups each represented by R902 are the same as or different from each other,
in the case where two or more groups each represented by R903 exist, the two or more groups each represented by R903 are the same as or different from each other,
in the case where two or more groups each represented by R904 exist, the two or more groups each represented by R904 are the same as or different from each other,
in the case where two or more groups each represented by R905 exist, the two or more groups each represented by R905 are the same as or different from each other,
in the case where two or more groups each represented by R906 exist, the two or more groups each represented by R906 are the same as or different from each other, and
in the case where two or more groups each represented by R907 exist, the two or more groups each represented by R907 are the same as or different from each other.
In one embodiment, the substituent for the case of “substituted or unsubstituted” may be a group selected from the group consisting of
an alkyl group having 1 to 50 carbon atoms,
an aryl group having 6 to 50 ring carbon atoms, and
a heterocyclic group having 5 to 50 ring atoms.
In one embodiment, the substituent for the case of “substituted or unsubstituted” may be a group selected from the group consisting of
an alkyl group having 1 to 18 carbon atoms,
an aryl group having 6 to 18 ring carbon atoms, and
a heterocyclic group having 5 to 18 ring atoms.
The specific examples of the groups for the arbitrary substituent described above are the specific examples of the substituent described in the section “Substituents in Description” described above.
In the description herein, the arbitrary adjacent substituents may form a “saturated ring” or an “unsaturated ring”, preferably form a substituted or unsubstituted saturated 5-membered ring, a substituted or unsubstituted saturated 6-membered ring, a substituted or unsubstituted unsaturated 5-membered ring, or a substituted or unsubstituted unsaturated 6-membered ring, and more preferably form a benzene ring, unless otherwise indicated.
In the description herein, the arbitrary substituent may further have a substituent unless otherwise indicated in the description. The definition of the substituent that the arbitrary substituent further has may be the same as the arbitrary substituent.
In the description herein, a numerical range shown by “AA to BB” means a range including the numerical value AA as the former of “AA to BB” as the lower limit value and the numerical value BB as the latter of “AA to BB” as the upper limit value.
The organic EL device of the present invention has a cathode, an anode, and organic layers intervening between the cathode and the anode, the organic layers including a light emitting layer and an electron transporting layer, the electron transporting layer containing a compound A, and the light emitting layer containing a host material B.
The compound A is represented by formula (1), and is used in the electron transporting layer,
wherein
one of Y1 and Y2 is a nitrogen atom and the other one is CR,
R is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group;
Ar1 and Ar2 each are independently selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms;
L1 and L2 each are independently a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms;
R1 to R6 each are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group,
adjacent two selected from R1 to R6 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
Cz is represented by the following formula (1-a) or formula (1-b):
wherein
R21 to R28 and R31 to R38 each are independently a hydrogen atom or a substituent, and the substituent is selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group
adjacent two selected from R21 to R28 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
adjacent two selected from R31 to R38 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
R24 and R25, and R34 and R35 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
Ra is selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms;
one selected from R21 to R28 is a single bond bonded to L3 via *a;
*b represents a position bonded to L3;
n is an integer of 1 to 3, and when n is an integer of 2 or 3, Cz's, which are 2 or 3, are the same or different from each other;
L3 and L4 each are independently a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms; provided that when n is 2 or 3, L4 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
The symbols in the formula (1) representing the compound A and the formulae described later will be explained below. Unless otherwise specified, the same symbols have the same meaning.
One of Y1 and Y2 is a nitrogen atom and the other one is CR. That is, Y1 is a nitrogen atom and Y2 is CR, or Y1 is CR and Y2 is a nitrogen atom.
n is an integer of 1 to 3, preferably 1 or 2, more preferably 1. When n is 2 or 3, the 2 or 3 Cz's are the same or different from each other.
R is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group. Preferably, R is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms. More preferably, R is a hydrogen atom.
The detail of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms is described in “Substituents in Description”, more preferably a phenyl group, a p-biphenyl group, an m-biphenyl group, an o-biphenyl group, a p-terphenyl-4-yl group, a p-terphenyl-3-yl group, a p-terphenyl-2-yl group, an m-terphenyl-4-yl group, an m-terphenyl-3-yl group, an m-terphenyl-2-yl group, an o-terphenyl-4-yl group, an o-terphenyl-3-yl group, an o-terphenyl-2-yl group, a 1-naphthyl group, a 2-naphthyl group, a fluorenyl group, a 9,9′-spirobifluorenyl group, a 9,9-dimethylfluorenyl group, or a 9,9-diphenylfluorenyl group, and further more preferably a phenyl group, a p-biphenyl group, an m-biphenyl group, an o-biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a fluorenyl group, a 9,9′-spirobifluorenyl group, a 9,9-dimethylfluorenyl group, or a 9,9-diphenylfluorenyl group.
The detail of the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms is described in “Substituents in Description”, more preferably a carbazolyl group (1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, or 9-carbazolyl group), a dibenzofuranyl group, a naphthobenzofuranyl group, a dibenzothiophenyl group, a naphthobenzothiophenyl group, a phenyldibenzofuranyl group, or a phenyldibenzothiophenyl group, and further more preferably a carbazolyl group (1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, or 9-carbazolyl group), a dibenzofuranyl group, or a dibenzothiophenyl group.
The detail of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms is described in “Substituents in Description”, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, or a t-butyl group, and more preferably a methyl group, an isopropyl group, or a t-butyl group.
The detail of the substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms is described in “Substituents in Description”, preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, and more preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.
R1 to R6 each are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group, preferably is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and more preferably is a hydrogen atom. R1 to R6 may all be hydrogen atoms.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and the substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms each are the same as the details of the corresponding groups described above with respect to R.
Adjacent two selected from R1 to R6, that is, at least one set of adjacent two selected from R1 and R2, R3 and R4, R4 and R5, and R5 and R6, may be bonded to each other to form a ring, or may not be bonded to each other and thus may not form a ring, preferably are not bonded to each other and thus do not form a ring.
The substituted or unsubstituted ring is selected from a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic heterocyclic ring, and a substituted or unsubstituted aliphatic heterocyclic ring, preferably a substituted or unsubstituted aromatic hydrocarbon ring.
The aromatic hydrocarbon ring is, for example, a benzene ring, a biphenylene ring, a naphthalene ring, an anthracene ring, a benzoanthracene ring, a phenanthrene ring, a benzophenanthrene ring, a phenalene ring, a pyrene ring, a chrysene ring, a 1,1-dimethylindene ring, or a triphenylene ring, preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.
The aliphatic hydrocarbon ring is, for example, a cyclopentene ring, a cyclopentadiene ring, a cyclohexene ring, a cyclohexadiene ring, or an aliphatic hydrocarbon ring obtained through partial hydrogenation of the aforementioned aromatic hydrocarbon rings.
The aromatic heterocyclic ring is, for example, a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, an imidazole ring, a pyrazole ring, an indole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a dibenzofuran ring, a naphthobenzofuran ring, a dibenzothiophene ring, a naphthobenzothiophene ring, a carbazole ring, or a benzocarbazole ring.
The aliphatic heterocyclic ring is, for example, an aliphatic heterocyclic ring obtained through partial hydrogenation of the aforementioned aromatic heterocyclic rings.
L3 and L4 each are independently a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
However, when n is an integer of 2 or 3, L4 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In an embodiment of the present invention, it is preferable that L3 and L4 each are independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In another embodiment of the present invention, it is preferable that L3 is a single bond and L4 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In further another embodiment of the present invention, it is preferable that L3 and L4 are single bonds.
The details of the substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms represented by L3 and L4 are described in “Substituents in Description”, and examples thereof include a divalent group derived by removing one hydrogen atom on the aromatic ring from the aforementioned “substituted or unsubstituted aryl group having 6 to 50 carbon atoms”.
Preferably, the unsubstituted arylene groups of the substituted or unsubstituted arylene groups having 6 to 50 ring carbon atoms represented by L3 and L4 each are independently selected from a phenylene group, a biphenylene group, a naphthylene group, a phenanthrylene group, an anthrasenylene group, and a fluoranthenylene group.
Ar1 and Ar2 each are independently selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms are the same as the details of the corresponding groups described above with respect to R.
It is preferable that the unsubstituted aryl groups of the substituted or unsubstituted aryl groups having 6 to 50 ring carbon atoms represented by Ar1 and Ar2 each are independently selected from a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, an anthrasenyl group, and a fluoranthenyl group.
The details of the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms are the same as the details of the corresponding groups described above with respect to R.
It is preferable that the unsubstituted heterocyclic groups of the substituted or unsubstituted heterocyclic groups having 5 to 50 ring atoms represented by Ar1 and Ar2 each are independently selected from a pyridyl group, a pyrimidinyl group, a triazinyl group, a quinolyl group, a di benzothiophenyl group, a dibenzofuranyl group, an azadibenzofuranyl group, and an azadibenzothiophenyl group.
L1 and L2 each are independently selected from a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In an embodiment of the present invention, it is preferable that one of L1 and L2 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, and the other one is a single bond.
In another embodiment of the present invention, it is preferable that L1 and L2 each are independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
In further another embodiment of the present invention, it is preferable that L1 and L2 are single bonds.
The details of the substituted or unsubstituted arylene group having 6 to 50 carbon atoms represented by L1 and L2 are the same as the details of the arylene group described above with respect to L3 and L4.
It is preferable that the unsubstituted arylene groups of the substituted or unsubstituted arylene groups having 6 to 50 ring carbon atoms represented by L1 and L2 each are independently selected from a phenylene group, a biphenylene group, a naphthylene group, and a phenanthrylene group.
Cz is a group represented by the following formula (1-a) or formula (1-b).
R21 to R28 and R31 to R38 each are independently a hydrogen atom or a substituent.
The substituent is selected from a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a fluorine atom, and a cyano group,
preferably, the substituent is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and more preferably, the substituent is a hydrogen atom.
One selected from R21 to R28, preferably R21, R22, R23, or R24, more preferably R23, is a single bond bonded to L3 via *a, and *b represents a position bonded to L3.
All of R21 to R28 that are not single bonds bonded to L3 via *a may be hydrogen atoms. In addition, R31 to R38 may all be hydrogen atoms.
Adjacent two selected from R21 to R28 that are not single bonds bonded to L3 via *a, that is, at least one set of adjacent two selected from R21 and R22, R22 and R23, R23 and R24, R25 and R26, R26 and R27, and R27 and R28 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring, preferably are not bonded to each other and thus do not form a ring.
R24 and R25 that are not single bonds bonded to L3 via *a may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring, preferably are not bonded to each other and thus do not form a ring.
Adjacent two selected from R31 to R38, that is, at least one set of adjacent two selected from R31 and R32, R32 and R33, R33 and R34, R35 and R36, R36 and R37, and R37 and R38 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring, preferably are not bonded to each other and thus do not form a ring.
R34 and R35 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring, preferably are not bonded to each other and thus do not form a ring.
The details of the substituted or unsubstituted rings are as described with respect to the rings arbitrarily formed by at least one set of adjacent two selected from R1 to R6.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and the substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms represented by R21 to R28 and R31 to R38 that are not single bonds bonded to L3 via *a each are the same as the details of the corresponding groups described above with respect to R.
The substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms is preferably a group not containing a 5-membered nitrogen-containing ring and a 7-membered nitrogen-containing ring. Examples of the heterocyclic group containing a 5-membered nitrogen-containing ring include a group containing a pyrrolidine structure, a pyrroline structure, a pyrrole structure, a carbazole structure, and a structure similar thereto. Examples of the heterocyclic group containing a 7-membered nitrogen-containing ring include a group containing an adipic structure, an adipan structure, and a structure similar thereto.
In an embodiment of the present invention, it is preferable that at least one selected from R21 to R28 that is not a single bond bonded to L3 via *a, or at least one selected from R31 to R38 is the substituent. The substituent is preferably a cyano group, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
It is preferable that the unsubstituted aryl groups of the substituted or unsubstituted aryl groups having 6 to 50 ring carbon atoms each independently is selected from a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group.
It is preferable that the unsubstituted alkyl group of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms is selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
Ra is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms each are the same as the details of the corresponding groups described above with respect to R.
It is preferable that the unsubstituted aryl group of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms represented by Ra is selected from a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group.
It is preferable that the unsubstituted alkyl group of the substituted or unsubstituted alkyl group having 1 to 50 ring carbon atoms represented by Ra is selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
In a preferred embodiment of the present invention, the compound A includes a compound represented by the formula (1-b-1) or (1-b-2).
In the formulae,
Y1, Y2, Ar1, Ar2, L1, L2, and R1 to R6 are defined in the formula (1),
R31 to R38 are defined in the formula (1-b),
R41 to R42, R44 to R45, R51 to R52, and R54 to R55 each are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms,
at least one set of adjacent two selected from R41 to R42, R44 to R45, R51 to R52 and R54 to R55 may be bonded to each other to form a substituted or unsubstituted benzene ring, or may not be bonded to each other and thus may not form a benzene ring.
R41, R42, R44, and R45 may all be hydrogen atoms. In addition, R51, R52, R54, and R55 may all be hydrogen atoms.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms represented by R41 to R42, R44 to R45, R51 to R52, and R54 to R55 each are the same as the details of the corresponding groups described above with respect to R.
In an embodiment of the present invention, it is preferable that at least one set of adjacent two selected from R41 and R42, and R44 and R45 may be bonded to each other to form a substituted or unsubstituted benzene ring. In another embodiment of the present invention, it is preferable not to form the benzene ring.
In an embodiment of the present invention, it is preferable that at least one set of adjacent two selected from R51 and R52, and R54 and R55 may be bonded to each other to form a substituted or unsubstituted benzene ring. In another embodiment of the present invention, it is preferable not to form the benzene ring.
In a preferred embodiment of the present invention, the compound A includes a compound represented by any of formulae (1-b-11) to (1-b-14).
In the formulae,
Y1, Y2, Ar1, Ar2, L1, L2, and R1 to R6 are defined in the formula (1),
R31 to R33 are defined in the formula (1-b),
R41, R44, and R45 are defined in the formula (1-b-1),
R43 is selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms.
The details of the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms and the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms represented by R43 are the same as the details of the corresponding groups described above with respect to R. All of R41 and R43 to R45 and all of two or three selected from R41 and R43 to R45 may be hydrogen atoms,
In a preferred embodiment of the present invention: the compound A includes a compound represented by any of formulae (1-a-1) to (1-a-4).
In the formulae,
Y1, Y2, Ar1, Ar2, L1, L2, and R1 to R6 are defined in the formula (1),
Ra and R21 to R28 are defined in the formula (1-a),
R41 to R42 and R44 to R45 are defined in the formula (1-b-1).
As described above, the “hydrogen atom” used in the description herein includes a protium atom, a deuterium atom, and a tritium atom. Accordingly, the compound A may contain a naturally-derived deuterium atom.
Further, a deuterium atom may be intentionally introduced into the compound A by using a deuterated compound as a part or all of the raw material compound. Accordingly, in one embodiment of the present invention, the compound A contains at least one deuterium atom. That is, the compound A may be a compound represented by the formula (1) or the aforementioned formula included in the formula (1) in which at least one hydrogen atom contained in the compound is a deuterium atom.
In the formula (1), at least one hydrogen atom selected from the following hydrogen atoms may be a deuterium atom: a hydrogen atom represented by R, R1 to R6, R21 to R28 that is not a single bond bonded to *a, and R31 to R38; a hydrogen atom of a substituent represented by R, R1 to R6, R21 to R28 that is not a single bond bonded to *a, and R31 to R38; a hydrogen atom of an arylene group represented by L1, L2, L3, and L4; a hydrogen of an aryl group or an alkyl group represented by Ra; and a hydrogen atom of an aryl group or a heterocyclic group represented by Ar1 and Ar2.
The deuteration rate of the deuterated compound A (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms in the compound A) depends on the deuteration rate of the raw material compound used. Since it is generally difficult to make the deuteration rates of all the raw material compounds used to 100%, the deuteration rate of the compound A is less than 100%, preferably 95% or less, more preferably 90% or less, and further more preferably 80% or less.
The deuteration rate of the compound A is 1% or more, preferably 3% or more, more preferably 5% or more, and further more preferably 10% or more.
The compound A may be a mixture of a deuterated compound (a compound having deuterium atoms intentionally introduced thereto) and a non-deuterated compound, or a mixture of two or more compounds having different deuteration rates from each other. The deuteration rate of the mixture (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms in the compound A contained in the mixture) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom represented by R or a hydrogen atom of a substituent represented by R may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of hydrogen atoms represented by R, or the number of all hydrogen atoms of the substituent represented by R) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom represented by R1 to R6 or a hydrogen atom of the substituent represented by R1 to R6 may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the total number of hydrogen atoms represented by R1 to R6 or all hydrogen atoms of the substituent represented by R1 to R6) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom represented by R21 to R28 that is not a single bond bonded to *a and a hydrogen atom of the substituent represented by R21 to R28 that is not a single bond bonded to *a may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the total number of hydrogen atoms represented by R21 to R28 that is not a single bond bonded to *a and hydrogen atoms of the substituent represented by R21 to R28 that is not a single bond bonded to *a) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%, preferably 95% or less, and more preferably 90% or less.
In the compound A, at least one hydrogen atom selected from a hydrogen atom represented by R31 to R38 and a hydrogen atom of the substituent represented by R31 to R38 may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the total number of hydrogen atoms represented by R31 to R38 and hydrogen atoms of the substituent represented by R31 to R38) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom of the arylene group represented by L1 and L2 may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the arylene group represented by L1 and L2) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom of the arylene group represented by L3 and L4 may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the arylene group represented by L3 and L4) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom of the aryl group represented by Ra may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the aryl group or the alkyl group represented by Ra) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the compound A, at least one hydrogen atom selected from a hydrogen atom of the aryl group or the heterocyclic group represented by Ar1 and Ar2 may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the aryl group or the heterocyclic group represented by Ar1 and Ar2) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
When each group of the compound A has a substituent, arbitrary substituents in the expression “substituted or unsubstituted” each are independently an aryl group having 6 to 50 ring carbon atoms, an alkyl group having 1 to 50 carbon atoms, or a cycloalkyl group having 3 to 50 ring carbon atoms.
The details of each arbitrary substituent are as described with respect to R in the formula (1).
The molecular weight of the compound A is preferably 650 or more, more preferably 650 to 5000, still more preferably 650 to 3000, and particularly preferably 650 to 2000. When the molecular weight is in this range, the performance of the organic EL device is improved.
The compound A can be readily produced by a person skilled in the art with reference to the following synthesis examples and the known synthesis methods.
Specific examples of the compound A will be described below; however, the compound A is not limited to the following compounds.
In the following specific examples, D represents a deuterium atom.
The host material B is represented by formula (10) and is used in the light emitting layer.
At least one selected from R101 to R110 in the formula (10), preferably R110 and R109, each independently, is a group represented by formula (31);
when there are two or more groups represented by the formula (31), the two or more groups represented by the formula (31) may be the same or different.
-L101-Ar101 (31)
L101 in the formula (31) is
a single bond,
a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms, preferably a single or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms:
Ar101 is
a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or
a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
One or more sets of adjacent two selected from R101 to R110 that are not groups represented by the formula (31) may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring.
R101 to R110, which are not groups represented by the formula (31) and do not form the ring, each independently are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, —Si(R901)(R902)(R903), —O—(R904), —S—(R905), —N(R906)(R907), a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms; more preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms.
R101 to R110, which are not groups represented by the formula (31) and do not form the ring, may all be hydrogen atoms.
R901 to R907 each independently is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms.
When two or more R901 to R907 are present, the two or more R901 to R907 may be the same or different.
In an embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-1):
wherein
R101 to R108, L101, and Ar101 are defined in the formula (10).
In another embodiment of the present: invention, the host material B represented by the formula (10) includes a compound represented by formula (10-2):
wherein
R101, R103 to R108, L101, and Ar101 are defined in the formula (10).
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-3):
wherein
R101A to R108A each are independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and R101A to R108A may all be hydrogen atoms:
L101A is a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms, and two R101A may be the same or different;
Ar101A is a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and two Arm may be the same or different.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-4):
wherein
L101 and R108A are defined in the formula (10),
R101A to R108A each independently are a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and R101A to R108A may all be hydrogen atoms;
X11 is O, S, or N(R61), preferably O or S;
R61 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
one of R62 to R69 is a single bond bonded to L101 via *;
at least one set of adjacent two selected from R62 to R69 that is not a single bond bonded to L101 may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
R62 to R69 that are not single bonds bonded to L101 and do not form the ring each independently are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and they may all be hydrogen atoms.
In another embodiment of the present invention, the host material. B represented by the formula, (10) includes a compound represented by formula (10-4A):
wherein
L101 and Ar101 are defined in the formula (10),
R101A to R108A each independently are a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and R101A to R108A may all be hydrogen atoms;
X11 is O, S or N(R61), preferably O or S;
R61 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, preferably a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms;
one set of adjacent two selected from R62A to R69A form a ring represented by formula (10-4A-1);
one or more sets of adjacent two selected from R62A to R69A that do not form a ring represented by the formula (10-4A-1) may be bonded to each other to form a substituted or unsubstituted ring, or may not be bonded to each other and thus may not form a ring;
R62A to R69A that do not form a ring represented by the formula (10-4A-1) and the other substituted or unsubstituted rings each independently are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and they may all be hydrogen atoms.
In the formula,
*1 and *2 each are boded to two ring carbon atoms to which the one set of adjacent two selected from R62A to R69A are bonded,
one of R70 to R73 is a single bond bonded to L101 via *,
R70 to R73, which are not single bonds bonded to L101, each independently are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and they may all be hydrogen atoms.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-6):
wherein
L101 and Ar101 are defined in the formula (10),
R101A to R108A are defined in the formula (10-4),
R66 to R69 are defined in the formula (10-4),
X12 is O or S.
In another embodiment of the present invention, the host material represented by the formula (10-6) includes a compound represented by formula (10-6H):
wherein
L101 and Ar101 are defined in the formula (10),
R66 to R69 are defined in the formula (10-4),
X12 is O or S.
In another embodiment of the present invention, the host material B represented by the formula (10-6) or the formula (10-6H) includes a compound represented by formula (10-6Ha):
wherein
L101 and Ar101 are defined in the formula (10),
X12 is O or S.
In another embodiment of the present invention, the host material B represented by the formula (10-6), (10-6H), or (10-6Ha) includes a compound represented by the following formula (10-6Ha-1) or (10-6Ha-2):
wherein
L101 and Ar101 are defined in the formula 10),
X12 is O or S.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-7):
wherein
L101 and Ar101 are defined in the formula (10),
R101A to R108A are defined in the formula (10-4),
X11 is defined in the formula (10-4),
R62 to R69 are defined in the formula (10-4), provided that one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are bonded to each other to form a substituted or unsubstituted ring,
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-7H):
wherein
L101 and Ar101 are defined in the formula (10),
X11 is defined in the formula (10-4),
R62 to R69 are defined in the formula (10-4), provided that one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are bonded to each other to form a substituted or unsubstituted ring.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-8):
wherein
L101 and Ar101 are defined in the formula (10),
R101A to R108A are defined in the formula (10-4),
X12 is O or S,
R66 to R69 are defined in the formula (10-4), provided that one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are bonded to each other to form a substituted or unsubstituted ring.
In another embodiment of the present invention, the host material B represented by the formula (10-8) includes a compound represented by formula (10-8H):
wherein
L101 and Ar101 are defined in the formula (10),
R66 to R69 are defined in the formula (10-4), presided that one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are bonded to each other to form a substituted or unsubstituted ring, preferably to form an unsubstituted benzene ring,
In another embodiment of the present invention, one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 of the formula (10-7), (10-7H), (10-8), or (10-8H) are bonded to each other to form a ring represented by formula (10-8-1) or formula (10-8-2), and R66 to R69 that do not form a ring represented by the formula (10-8-1) or formula (10-8-2) do not form a ring.
In the formulae,
two * each are bonded to two ring carbon atoms to which the one set of adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are bonded,
R80 to R83 each independently are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, and R80 to R83 may all be hydrogen atoms,
X13 is O or S.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formula (10-9):
wherein
L101 and Ar101 are defined in the formula (10),
R101A to R108A are defined in the formula (10-4),
R66 to R69 are defined in the formula (10-4), provided that adjacent two selected from R66 and R67, R67 and R68, and R68 and R69 are not bonded to each other and thus do not form a ring,
X12 is O or S.
In another embodiment of the present invention, the host material B represented by the formula (10) includes a compound represented by formulae (10-10-1) to (10-10-4):
wherein
L101A, Ar101A, and R101A to R108A are definer in the formula (10-3).
In another embodiment of the present invention, the host material B represented by the formulae (10-10-1) to (10-10-4) includes a compound represented by formulae (10-10-1H) to (10-10-4H):
wherein
L101A and Ar101A are defined in the formula (10-3).
Unless otherwise specified, the details of the ring formed by adjacent two included in the formula (10) and other formulae representing the host material B are as described with respect to the ring formed by adjacent two of the formula (1), and preferably a benzene ring, a benzofuran ring, or a benzothiophene ring.
The details of each substituent included in the formula (10) and other formulae representing the host material B are as described in the column of “Substituents in Description”.
In the formula (10) and other formulae representing the host material B, the halogen atom is preferably a fluorine atom.
In the formula (10) and other formulae representing the host material B, the unsubstituted alkyl group of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, or a t-butyl group, more preferably a methyl group, an isopropyl group, or a t-butyl group.
In the formula (10) and other formulae representing the host material B, the unsubstituted alkenyl group of the substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms is preferably a vinyl group or an allyl group.
In the formula (10) and other formulae representing the host material B, the unsubstituted alkynyl group of the substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms is preferably an ethynyl group.
In the formula (10) and other formulae representing the host material B, the unsubstituted cycloalkyl group of the substituted or unsubstituted cycloalkyl group having 3 to 50 ring carbon atoms is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group, more preferably a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group.
In the formula (10) and other formulae representing the host material B, —Si(R901)(R902)(R903) is a mono-, di-, or tri-substituted silyl group, preferably a tri-substituted silyl group, more preferably a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a propyldimethylsilyl group, an isopropyldimethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a t-butyldiphenylsilyl group, or a tritrylsilyl group.
In the formula (10) and other formulae representing the host material B, —O—(R904) is a substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, preferably a methoxy group, an ethoxy group, an isopropoxy group, an s-propoxy group, a t-butoxy group, a phenoxy group, or a biphenyloxy group.
In the formula (10) and other formulae representing the host material B, —S—(R905) is a substituted or unsubstituted alkylthio group or a substituted or unsubstituted arylthio group, preferably a methylthio group, an ethylthio group, an isopropylthio group, an s-propylthio group, a t-butylthio group, a phenylthio group, or a biphenylthio group.
In the formula (10) and other formulae representing the host material B, —N(R906)(R907) is a mono- or di-substituted amino group, preferably a di-substituted amino group, more preferably a dimethylamino group or a diethylamino group, a diisopropylamino group, or a diphenylamino group.
In the formula (10) and other formulae representing the host material B, the substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms is preferably a phenyl group, a biphenyl group, a terphenyl, a naphthyl group, a phenanthryl group, a benzophenanthryl group, a pyrenyl group, a triphenylenyl group, a benzotriphenylenyl group, a 9,9-dimethylfluorenyl group, a benzo-9,9-dimethylfluorenyl group, a 9,9-diphenylfluorenyl group, or a 9,9′-spirobifluorenyl group.
In the formula (10) and other formulae representing the host material B, the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms is preferably a pyridyl group, a pyrimidinyl group, a triazinyl group, a dibenzofuranyl group, a benzodibenzofuranyl group, a benzofurodibenzofuranyl group, a dibenzothiophenyl group, a benzodibenzothiophenyl group, a 9-carbazolyl group, or a 9-phenylcarbazolyl group.
In the formula (10) and other formulae representing the host material B, the substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms is preferably a phenylene group (o-phenylene group, m-phenylene group, p-phenylene group), a naphthylene group (1,3-naphthylene group, 1,4-naphthylene group, 2,6-naphthylene group), an anthrylene group (9,10-anthrylene group), or a 9,9-dimethylfluorene-2,7-diyl group.
In the formula (10) and other formulae representing the host material B, an unsubstituted divalent heterocyclic group of the substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring atoms is preferably a divalent residue of an aromatic heterocyclic ring selected from pyridine, pyrimidine, triazine, carbazole, benzocarbazole, benzofuran, dibenzofuran, naphthobenzofuran, benzothiophene, and dibenzothiophene.
When each group of the host material B has a substituent, arbitrary substituents in the expression “substituted or unsubstituted” each are independently an aryl group having 6 to 50 ring carbon atoms, an alkyl group having 1 to 50 carbon atoms, or a cycloalkyl group having 3 to 50 ring carbon atoms.
The details of each arbitrary substituent are as described with respect to R in the formula (1).
Similar to the case of the compound A, the host material B may contain a naturally-derived deuterium atom. Further, a deuterium atom may be intentionally introduced into the host material B by using a deuterated compound as a part or all of the raw material compound. Accordingly, in one embodiment of the present invention, the host material B contains at least one deuterium atom. That is, the host material B may be a compound represented by the formula (10) or the aforementioned formula included in the formula (10) in which at least one hydrogen atom contained in the compound is a deuterium atom.
In the formula (10), at least one hydrogen atom selected from the following hydrogen atoms may be a deuterium atom: a hydrogen atom contained in a ring arbitrarily formed by one or more sets of adjacent two selected from R101 to R110 that are not groups represented by the formula (31); a hydrogen atom represented by R101 to R110 that is not a group represented by the formula (31) and does not form the ring; a hydrogen atom of a substituent represented by R101 to R110 that is not a group represented by the formula (31) and does not form the ring; a hydrogen atom of an arylene group or a heterocyclic group represented by L101 of the formula (31); and a hydrogen of an aryl group or a heterocyclic group represented by Ar101 of the formula (31).
The deuteration rate of the deuterated host material B (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms in the host material B) depends on the deuteration rate of the raw material compound used. Since it is generally difficult to make the deuteration rates of all the raw material compounds used to 100%, the deuteration rate of the host material B is less than 100%, preferably 95% or less, more preferably 90% or less, and further more preferably 80% or less.
The deuteration rate of the deuterated host material B is 1% or more, preferably 3% or more, more preferably 5% or more, and further more preferably 10% or more.
The host material B may be a mixture of a deuterated compound (a compound having deuterium atoms intentionally introduced thereto) and a non-deuterated compound, or a mixture of two or more compounds having different deuteration rates from each other. The deuteration rate of the mixture (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms in the host material B contained in the mixture) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the host material B represented by the formula (10), at least one hydrogen atom selected from a hydrogen atom contained in a ring arbitrarily formed by one or more sets of adjacent two selected from R101 to R110 that are not groups represented by the formula (31) may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the total number of hydrogen atoms of the arbitrarily formed ring) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the host material B represented by the formula (10), at least one hydrogen atom selected from a hydrogen atom represented by R101 to R110 that is not a group represented by the formula (31) and does not form the ring and a hydrogen atom contained in a substituent represented by R101 to R110 that are not groups represented by the formula (31) and do not form the ring may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the total number of hydrogen atoms represented by R101 to R110 that are not groups represented by the formula (31) and do not form the ring and hydrogen atoms contained in a substituent represented by R101 to R110 that are not groups represented by the formula (31) and do not form the ring) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the host material B represented by the formula (10), at least one hydrogen atom selected from a hydrogen atom of the arylene group or the heterocyclic group represented by L101 of the formula (31) may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the arylene group or the heterocyclic group represented by L101) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
In the host material B represented by the formula (10), at least one hydrogen atom selected from a hydrogen atom of the arylene group or the heterocyclic group represented by Ar101 of the formula (31) may be a deuterium atom. The deuteration rate (the proportion of the number of deuterium atoms with respect to the number of all hydrogen atoms of the arylene group or the heterocyclic group represented by Ar101) is 1% or more, preferably 3% or more, more preferably 5% or more, and still more preferably 10% or more, and is less than 100%.
The host material B is a known compound and can be readily produced with reference to a known synthesis method.
Specific examples of the host material B will be described below; however, the compound A is not limited to the following compounds.
The organic EL device of the present invention includes an anode, a cathode, and organic layers intervening between the anode and the cathode. The organic layers include an electron transporting layer and a light emitting layer, the electron transporting layer contains the compound A and the light emitting layer contains the host material B.
The organic EL device of the present invention may be a fluorescent or phosphorescent light emission-type monochromatic light emitting device or a fluorescent/phosphorescent hybrid-type white light emitting device, and may be a simple type having a single light emitting unit or a tandem type having a plurality of light emitting units. The “light emitting unit” referred to herein refers to a minimum unit that emits light through recombination of injected holes and electrons, which includes organic layers among which at least one layer is a light emitting layer.
For example, as a representative device configuration of the simple type organic EL device, the following device configuration may be exemplified.
The light emitting unit may be a multilayer type having a plurality of phosphorescent light emitting layers or fluorescent light emitting layers. In this case, a space layer may intervene between the light emitting layers for the purpose of preventing excitons generated in the phosphorescent light emitting layer from diffusing into the fluorescent light emitting layer. Representative layer configurations of the simple type light emitting unit are described below. Layers in parentheses are optional.
(a) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(b) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(c) (hole injecting layer/) hole transporting layer/first fluorescent light emitting layer/second fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(d) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(e) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(f) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/second phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(g) (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer/space layer/second phosphorescent light emitting layer/space layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(h) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/space layer/first fluorescent light emitting layer/second fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(i) (hole injecting layer/) hole transporting layer/electron blocking layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(j) (hole injecting layer/) hole transporting layer/electron blocking layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(k) (hole injecting layer/) hole transporting layer/exciton blocking layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(l) (hole injecting layer/) hole transporting layer/exciton blocking layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(m) (hole injecting layer/) first hole transporting layer/second hole transporting layer/fluorescent light emitting layer/electron transporting layer (/electron injecting layer)
(n) (hole injecting layer/) first hole transporting layer/second hole transporting layer/phosphorescent light emitting layer/electron transporting layer (/electron injecting layer)
(o) (hole injecting layer/) first hole transporting layer/second hole transporting layer/fluorescent light emitting layer/first electron transporting layer/second electron transporting layer (/electron injecting layer)
(p) (hole injecting layer/) first hole transporting layer/second hole transporting layer/phosphorescent light emitting layer/first electron transporting layer/second electron transporting layer (/electron injecting layer)
(q) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
(r) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
(s) (hole injecting layer/) hole transporting layer/fluorescent light emitting layer/exciton blocking layer/electron transporting layer (/electron injecting layer)
(t) (hole injecting layer/) hole transporting layer/phosphorescent light emitting layer/exciton blocking layer/electron transporting layer (/electron injecting layer)
(u) (hole injecting layer/) hole transporting layer/electron blocking layer/phosphorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
(v) (hole injecting layer/) hole transporting layer/electron blocking layer/phosphorescent light emitting layer/hole blocking layer/electron transporting layer (/electron injecting layer)
The phosphorescent and fluorescent light emitting layers each can emit emission colors different from each other. Specifically, in the light emitting unit (f), a layer configuration, such as (hole injecting layer/) hole transporting layer/first phosphorescent light emitting layer (red light emission)/second phosphorescent light emitting layer (green light emission)/space layer/fluorescent light emitting layer (blue light emission)/electron transporting layer, may be exemplified.
An electron blocking layer may be properly provided between each light emitting layer and the hole transporting layer or the space layer. Further, a hole blocking layer may be properly provided between each light emitting layer and the electron transporting layer. The employment of the electron blocking layer or the hole blocking layer allows improving the emission efficiency by trapping electrons or holes within the light emitting layer and increasing the probability of charge recombination in the light emitting layer.
As a representative device configuration of the tandem type organic EL device, the following device configuration may be exemplified.
Here, for example, each of the first light emitting unit and the second light emitting unit may be independently selected from the above-described light emitting units.
The intermediate layer is also generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron withdrawing layer, a connecting layer, or an intermediate insulating layer, and a known material configuration, in which electrons are supplied to the first light emitting unit and holes are supplied to the second light emitting unit, can be used.
In the present invention, a host combined with a fluorescent dopant (a fluorescent light emitting material) is referred to as a fluorescent host, and a host combined with a phosphorescent dopant is referred to as a phosphorescent host. The fluorescent host and the phosphorescent host are not distinguished from each other merely by the molecular structures thereof. That is, the phosphorescent host means a material that forms a phosphorescent light emitting layer containing a phosphorescent dopant, and does not mean unavailability as a material that forms a fluorescent light emitting layer. The same also applies to the fluorescent host.
The substrate is used as a support of the organic EL device. Examples of the substrate include a plate of glass, quartz, and plastic. In addition, a flexible substrate may be used. Examples of the flexible substrate include a plastic substrate made of polycarbonate, polyarylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, or polyvinyl chloride. In addition, an inorganic vapor deposition film can be used.
It is preferable that a metal, an alloy, an electrically conductive compound, and a mixture thereof, which has a high work function (specifically 4.0 eV or more) is used for the anode formed on the substrate. Specific examples thereof include indium oxide-tin oxide (ITO: Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide and zinc oxide, and graphene. In addition, examples thereof include gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides of the metals (for example, titanium nitride).
These materials are usually deposited by a sputtering method. For example, through a sputtering method, it is possible to form indium oxide-zinc oxide by using a target in which 1 to 10 wt % of zinc oxide is added to indium oxide, and to form indium oxide containing tungsten oxide and zinc oxide by using a target containing 0.5 to 5 wt % of tungsten oxide and 0.1 to 1 wt % of zinc oxide with respect to indium oxide. In addition, the production may be performed by a vacuum vapor deposition method, a coating method, an inkjet method, a spin coating method, or the like.
The hole injecting layer formed in contact with the anode is formed by using a material that facilitates hole injection regardless of a work function of the anode, and thus it is possible to use materials generally used as an electrode material (for example, metals, alloys, electrically conductive compounds, and mixtures thereof, elements belonging to Group 1 or Group 2 of the periodic table of the elements).
It is also possible to use elements belonging to Group 1 or Group 2 of the periodic table of the elements, which are materials having low work functions, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), and alloys containing these (such as MgAg and AlLi), as well as rare earth metals such as europium (Eu) and ytterbium (Yb), and alloys containing these. When the anode is formed by using the alkali metals, the alkaline earth metals, and alloys containing these, a vacuum vapor deposition method or a sputtering method can be used. Further, when a silver paste or the like is used, a coating method, an inkjet method, or the like can be used.
The hole injecting layer is a layer containing a material having a high hole injection capability (a hole injecting material) and is provided between the anode and the light emitting layer, or between the hole transporting layer, if exists, and the anode.
As the hole injecting material, molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, and the like can be used.
Examples of the hole injecting layer material also include aromatic amine compounds as low-molecular weight organic compounds, such as 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), 4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), and 3-[N-(1-naphthyl)-N-(9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1).
High-molecular weight compounds (such as oligomers, dendrimers, and polymers) may also be used. Examples thereof include high-molecular weight compounds, such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide] (abbreviation: PTPDMA), and poly[N, N′-bis(4-butylphenyl)-N, N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD). In addition, high-molecular weight compounds to which an acid, such as poly(3,4-ethylenedioxythiophene)/poly (styrene sulfonic acid) (PEDOT/PSS) and polyaniline/poly (styrenesulfonic acid) (PAni/PSS), is added, can also be used.
Furthermore, it is also preferable to use an acceptor material, such as a hexaazatriphenylene (HAT) compound represented by the following formula (K),
wherein
R21 to R26 each independently represent a cyano group, —CONH2, a carboxy group, or —COOR27 (R27 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms). In addition, adjacent two selected from R21 and R22, R23 and R24, and R25 and R26 may be bonded to each other to form a group represented by —CO—O—CO—.
Examples of R27 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, and a cyclohexyl group.
The hole transporting layer is a layer containing a material having a high hole transporting capability (a hole transporting material) and is provided between the anode and the light emitting layer, or between the hole injecting layer, if exists, and the light emitting layer.
The hole transporting layer may have a single layer structure or a multilayer structure including two or more layers. For example, the hole transporting layer may have a two-layer structure including a first hole transporting layer (anode side) and a second hole transporting layer (cathode side). In one embodiment of the present invention, the hole transporting layer having a single layer structure is preferably disposed adjacent to the light emitting layer, and the hole transporting layer that is closest to the cathode in the multilayer structure, such as the second hole transporting layer in the two-layer structure, is preferably disposed adjacent to the light emitting layer. In another embodiment of the present invention, an electron blocking layer described later and the like may be disposed between the hole transporting layer having a single layer structure and the light emitting layer, or between the hole transporting layer that is closest to the light emitting layer in the multilayer structure and the light emitting layer.
As the hole transporting layer material, for example, an aromatic amine compound, a carbazole derivative, an anthracene derivative, and the like can be used.
Examples of the aromatic amine compound include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BAFLP), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB). The aforementioned compounds have a hole mobility of 10−6 cm2/Vs or more.
Examples of the carbazole derivative include 4,4′-di(9-carbazolyl)biphenyl (abbreviation: CBP), 9-[4-(9-carbazolyl)phenyl]-10-phenylanthracene (abbreviation: CzPA), and 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: PCzPA).
Examples of the anthracene derivative include 2-t-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), and 9,10-diphenylanthracene (abbreviation: DPAnth).
High-molecular weight compounds, such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA), can also be used.
However, compounds other than those as mentioned above can also be used as long as they are compounds high in the hole transporting capability rather than in the electron transporting capability.
The light emitting layer is a layer containing a material having a high light emitting property (a dopant material), and various materials can be used. For example, a fluorescent light emitting material or a phosphorescent light emitting material can be used as the dopant material. The fluorescent light emitting material is a compound that emits light from a singlet excited state, and the phosphorescent light emitting material is a compound that emits light from a triplet excited state.
Examples of a blue-based fluorescent light emitting material that can be used for the light emitting layer include a pyrene derivative, a styrylamine derivative, a chrysene derivative, a fluoranthene derivative, a fluorene derivative, a diamine derivative, and a triarylamine derivative. Specific examples thereof include N,N′-bis[4-(9H-carbazole-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S), 4-(9H-carbazole-9-yl)-4′-(10-phenyl anthryl)triphenylamine (abbreviation: YGAPA), and 4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBAPA).
Examples of a green-based fluorescent light emitting material that can be used for the light emitting layer include an aromatic amine derivative. Specific examples thereof include N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl anthryl)-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N-[9,10-bis(1,1′-biphenyl-2-yl)]-N-[4-(9H-carbazole-9-yl)phenyl]-N-phenylanthracene-2-amine (abbreviation: 2YGABPhA), and N,N,9-triphenylanthracene-9-amine (abbreviation: DPhAPhA).
Examples of a red-based fluorescent light emitting material that can be used for the light emitting layer include a tetracene derivative and a diamine derivative. Specific examples thereof include N,N, N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD) and 7,14-diphenyl-N,N,N′,N′-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD).
Examples of a blue-based phosphorescent light emitting material that can be used for the light emitting layer include a metal complex, such as an iridium complex, an osmium complex, and a platinum complex. Specific examples thereof include bis[2-(4′,6′-difluorophenyppyridinato-N,C2′]iridium(III)tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]iridium(III)picolinate (abbreviation: Flrpic), bis[2-(3′,5′bistrifluoromethylphenyppyridinato-N,C2′]iridium(III)picolinate (abbreviation: Ir(CF3ppy)2(pic)), and bis[2-(4′,6′-difluorophenyl)pyridinato-N,C2′]ridium(III)acetylacetonate (abbreviation: Flracac).
Examples of a green-based phosphorescent light emitting material that can be used for the light emitting layer include an iridium complex. Examples thereof include tris(2-phenylpyridinato-N,C2′)iridium(III) (abbreviation: Ir(ppy)3), bis(2-phenylpyridinato-N,C2′)iridium(III)acetylacetonate (abbreviation: Ir(ppy)2(acac)), bis(1,2-diphenyl-1H-benzimidazolato)iridium(III)acetylacetonate (abbreviation: Ir(pbi)2(acac)), and bis(benzo[h]quinolinato)iridium(III)acetylacetonate (abbreviation: Ir(bzq)2(acac)).
Examples of a red-based phosphorescent light emitting material that can be used for the light emitting layer include a metal complex, such as an iridium complex, a platinum complex, a terbium complex, and a europium complex. Specific examples thereof include organic metal complexes, such as bis[2-(2′-benzo[4,5-α]thienyl)pyridinato-N,C3′]iridium(III)acetylacetonate (abbreviation: Ir(btp)2(acac)), bis(1-phenylisoquinolinato-N,C2′)iridium(III)acetylacetonate (abbreviation: Ir(piq)2(acac)), (acetylacetonate)bis[2,3-bis(4-fluorophenyl)quinoxalinato] iridium(III) (abbreviation: Ir(Fdpq)2(acac)), and 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrinplatinum(II) (abbreviation: PtOEP).
In addition, rare earth metal complexes, such as tris(acetylacetonate) (monophenanthroline)terbium(III) (abbreviation: Tb(acac)3(Phen)), tris(1,3-diphenyl-1,3-propanedionate)(monophenanthroline)europium(III) (abbreviation: Eu(DBM)3(Phen)), and tris[1-(2-thenoyl)-3,3,3-trifluoroacetonate](monophenanthroline)europium(III) (abbreviation: Eu(TTA)3(Phen)), emit light from rare earth metal ions (electron transition between different multiplicities), and thus may be used as the phosphorescent light emitting material.
The light emitting layer may have a configuration in which the aforementioned dopant material is dispersed in another material (a host material). The host material is preferably a material that has a higher lowest unoccupied orbital level (LUMO level) and a lower highest occupied orbital level (HOMO level) than the dopant material.
In the organic EL device of the present invention, the host material B is used as the host material for the light emitting layer.
In one embodiment of the present invention, the host material B contained in the light emitting layer contains at least one deuterium atom. Further, the host material B may be a mixture of a host material B in which all hydrogen atoms are protium atoms (hereinafter referred to as “light hydrogen body”) and a host material B in which at least one of all hydrogen atoms is a deuterium atom (heavy hydrogen body). However, the light hydrogen body may contain deuterium atoms in a proportion equal to or less than the natural abundance ratio.
In an embodiment of the present invention, the host material B contained in the light emitting layer is preferably a light hydrogen body from the viewpoint of production cost. Therefore, the present invention includes an organic EL device in which the light emitting layer contains a host material B substantially composed of only a light hydrogen body. The “host material B substantially composed of only a light hydrogen body” means that the content ratio of the light hydrogen body to the total amount of the host material B is 90 mol % or more, preferably 95 mol % or more, more preferably 99 mol % or more (each including 100%).
In addition to the host material B, other host materials may be used. Examples of the other host materials include:
(1) a metal complex, such as an aluminum complex, a beryllium complex, and a zinc complex,
(2) a heterocyclic compound, such as an oxadiazole derivative, a benzimidazole derivative, and a phenanthroline derivative,
(3) a fused aromatic compound, such as a carbazole derivative, an anthracene derivative, a phenanthrene derivative, a pyrene derivative, and a chrysene derivative, or
(4) an aromatic amine compound, such as a triarylamine derivative and a fused polycyclic aromatic amine derivative.
For example,
metal complexes, such as tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum(III) (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ);
heterocyclic compounds, such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), and bathophenanthroline (abbreviation: BPhen), and bathocuproine (abbreviation: BCP);
fused aromatic compounds, such as 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA), 3,6-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: DPCzPA), 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 9,9′-bianthryl(abbreviation: BANT), 9,9′-(stilbene-3,3′-diyl)diphenanthrene (abbreviation: DPNS), 9,9′-(stilbene-4,4′-diyl)diphenanthrene (abbreviation: DPNS2), 3,3′,3″-(benzene-1,3,5-triyl)tripyrene (abbreviation: TPB3), 9,10-diphenylanthracene (abbreviation: DPAnth), and 6,12-dimethoxy-5,11-diphenylchrysene; and
aromatic amine compounds, such as N,N-diphenyl-9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole-3-amine (abbreviation: CzA1PA), 4-(10-phenyl-9-anthryl)triphenylamine (abbreviation: DPhPA), N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole-3-amine (abbreviation: PCAPA), N,9-diphenyl-N-{4-[4-(10-phenyl-9-anthryl)phenyl]phenyl}-9H-carbazole-3-amine (abbreviation: PCAPBA), N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB or a-NPD), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB) can be used.
The electron transporting layer is a layer containing a material having a high electron transporting capability (an electron transporting material) and is provided between the light emitting layer and the cathode, or between the electron injecting layer, if exists, and the light emitting layer.
The electron transporting layer may have a single layer structure or a multilayer structure. For example, the electron transporting layer may have a two-layer structure including a first electron transporting layer (anode side) and a second electron transporting layer (cathode side). In one embodiment of the present invention, the electron transporting layer having a single layer structure is preferably disposed adjacent to the light emitting layer, and the electron transporting layer that is closest to the anode in the multilayer structure, such as the first electron transporting layer in the two-layer structure, is preferably disposed adjacent to the light emitting layer. In another embodiment of the present invention, a hole blocking layer described later and the like may be disposed between the electron transporting layer having a single layer structure and the light emitting layer, or between the electron transporting layer that is closest to the light emitting layer in the multilayer structure and the light emitting layer.
The organic EL device of the present invention contains the compound Ain the electron transporting layer.
In the electron transporting layer having a two-layer structure, the compound A may be contained in one of the first electron transporting layer and the second electron transporting layer, and may also be contained in both of the first electron transporting layer and the second electron transporting layer.
In one embodiment of the present invention, the compound A is contained only in the first electron transporting layer, and the second electron transporting layer contains an electron transporting layer material other than the compound A.
In another embodiment, the compound A is contained only in the second electron transporting layer, and the first electron transporting layer contains an electron transporting layer material other than the compound A.
In still another embodiment, the compound A is contained in the first electron transporting layer and the second electron transporting layer. One or both of the first electron transporting layer and the second electron transporting layer may contain an electron transporting layer material other than the compound A.
In one embodiment of the present invention, the compound A contains at least one deuterium atom. Further, the compound A may be a mixture of a host compound A in which all hydrogen atoms are protium atoms (hereinafter referred to as “light hydrogen body”) and a compound Ain which at least one of all hydrogen atoms is a deuterium atom (heavy hydrogen body). However, the light hydrogen body may contain deuterium atoms in a proportion equal to or less than the natural abundance ratio.
In an embodiment of the present invention, the compound A contained in the electron transporting layer (including the first electron transporting layer and the second electron transporting layer) is preferably a light hydrogen body from the viewpoint of production cost.
Therefore, the present invention includes an organic EL device in which the electron transporting layer contains a compound A substantially composed of only a light hydrogen body. The “compound A substantially composed of only a light hydrogen body” means that the content ratio of the light hydrogen body to the total amount of the compound A is 90 mol % or more, preferably 95 mol % or more, more preferably 99 mol % or more (each including 100%).
In addition to the compound A, other electron transporting layer materials may be used. Examples of the other electron transporting layer materials include:
(1) a metal complex, such as an aluminum complex, a beryllium complex, and a zinc complex;
(2) a heteroaromatic compound, such as an imidazole derivative, a benzimidazole derivative, an azine derivative, a carbazole derivative, and a phenanthroline derivative; and
(3) a high-molecular weight compound.
Examples of the metal complex include tris(8-quinolinolato)aluminum(III) (abbreviation: Alq), tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato(beryllium (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato) (4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ).
Examples of the heteroaromatic compound include 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), and 4,4′-bis(5-methylbenzxazol-2-yl)stilbene (abbreviation: BzOs).
Examples of the high-molecular weight compound include poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)] (abbreviation: PF-Py), and poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy).
The materials are materials having an electron mobility of 10−6 cm2/Vs or more. Materials other than those as mentioned above may also be used in the electron transporting layer as long as they are materials high in the electron transporting capability rather than in the hole transporting capability.
The electron injecting layer is a layer containing a material having a high electron injection capability. In the electron injecting layer, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), rare earth metals such as europium (Eu) and ytterbium (Yb), and compounds containing these metals can be used. Examples of the compounds include an alkali metal oxide, an alkali metal halide, an alkali metal-containing organic complex, an alkaline earth metal oxide, an alkaline earth metal halide, an alkaline earth metal-containing organic complex, a rare earth metal oxide, a rare earth metal halide, and a rare earth metal-containing organic complex. Further, these compounds may be used as a mixture of a plurality thereof.
In addition, a material having an electron transporting capability, in which an alkali metal, an alkaline earth metal, or a compound thereof is contained, specifically Alq in which magnesium (Mg) is contained may be used. In this case, electron injection from the cathode can be more efficiently performed.
Otherwise, in the electron injecting layer, a composite material obtained by mixing an organic compound with an electron donor may be used. Such a composite material is excellent in the electron injection capability and the electron transporting capability because the organic compound receives electrons from the electron donor. In this case, the organic compound is preferably a material excellent in transporting received electrons, and specifically, for example, a material constituting the aforementioned electron transporting layer (such as a metal complex and a heteroaromatic compound) can be used. As the electron donor, a material having an electron donation property for the organic compound may be used. Specifically, alkali metals, alkaline earth metals, and rare earth metals are preferred, and examples thereof include lithium, cesium, magnesium, calcium, erbium, and ytterbium. In addition, an alkali metal oxide or an alkaline earth metal oxide is preferred, and examples thereof include lithium oxide, calcium oxide, and barium oxide. In addition, a Lewis base, such as magnesium oxide, can also be used. In addition, an organic compound, such as tetrathiafulvalene (abbreviation: TTF), can also be used.
It is preferable that a metal, an alloy, an electrically conductive compound, and a mixture thereof, which has a low work function (specifically 3.8 eV or less) is used for the cathode. Specific examples of such a cathode material include elements belonging to Group 1 or Group 2 of the periodic table of the elements, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), calcium (Ca), and strontium (Sr), as well as alloys containing these (such as MgAg, and AlLi), rare earth metals such as europium (Eu), and ytterbium (Yb), and alloys containing these.
When the cathode is formed by using the alkali metals, the alkaline earth metals, and the alloys containing these, a vacuum vapor deposition method or a sputtering method can be used. In addition, when a silver paste or the like is used, a coating method, an inkjet method, or the like can be used.
By providing the electron injecting layer, the cathode can be formed using various conductive materials, such as Al, Ag, ITO, graphene, and indium oxide-tin oxide containing silicon or silicon oxide regardless of the magnitude of a work function. These conductive materials can be deposited by using a sputtering method, an inkjet method, a spin coating method, or the like.
The organic EL device applies an electric field to an ultrathin film, and thus pixel defects are likely to occur due to leaks or short-circuiting. In order to prevent it, an insulating layer formed of an insulating thin film layer may be inserted between a pair of electrodes.
Examples of the material used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture or a laminate of these may also be used.
The space layer is, for example, a layer provided between a fluorescent light emitting layer and a phosphorescent light emitting layer for the purpose of preventing excitons generated in the phosphorescent light emitting layer from diffusing into the fluorescent light emitting layer, or adjusting a carrier balance, in the case where the fluorescent light emitting layers and the phosphorescent light emitting layers are laminated. In addition, the space layer can also be provided among a plurality of phosphorescent light emitting layers.
Since the space layer is provided between the light emitting layers, a material having both an electron transporting capability and a hole transporting capability is preferable. Also, one having a triplet energy of 2.6 eV or more is preferable in order to prevent triplet energy diffusion in an adjacent phosphorescent light emitting layer. Examples of the material used for the space layer include the same materials as those used for the hole transporting layer as described above.
The blocking layer, such as the electron blocking layer, the hole blocking layer, and the exciton blocking layer, may be provided adjacent to the light emitting layer. The electron blocking layer is a layer that prevents electrons from leaking from the light emitting layer to the hole transporting layer, and the hole blocking layer is a layer that prevents holes from leaking from the light emitting layer to the electron transporting layer. The exciton blocking layer has a function of preventing excitons generated in the light emitting layer from diffusing into the surrounding layers, and trapping the excitons within the light emitting layer.
Each layer of the organic EL device may be formed by a conventionally known vapor deposition method, a coating method, or the like. For example, each layer can be formed by a known method using a vapor deposition method such as a vacuum vapor deposition method and a molecular beam vapor deposition method (MBE method), or a coating method using a solution of a compound forming a layer, such as a dipping method, a spin-coating method, a casting method, a bar-coating method, and a roll-coating method.
The film thickness of each layer is not particularly limited, but is preferably 5 nm to 10 μm, and more preferably 10 nm to 0.2 μm because in general, when the film thickness is too small, defects such as pinholes are likely to occur, and conversely, when the film thickness is too large, a high driving voltage is required and the efficiency decreases.
The organic EL device can be used in electronic devices, such as display components of an organic EL panel module and the like, display devices of a television, a mobile phone, a personal computer, and the like, and light emitting devices of lightings and vehicular lamps.
Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples.
Each organic EL device was produced in the following manner, and each device was evaluated for the EL device performance.
A glass substrate of 25 mm×75 mm×1.1 mm provided with an ITO transparent electrode (anode) (manufactured by GEOMATEC Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes and then subjected to UV ozone cleaning for 30 minutes. The film thickness of the ITO was 130 mu.
The cleaned glass substrate provided with the ITO transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and firstly Compound HT-1 and Compound HI-1 were vapor co-deposited on a surface having the transparent electrode formed thereon, so as to cover the transparent electrode, resulting in a hole injecting layer with a film thickness of 10 nm. The mass ratio of Compound HT-1 and Compound HI-1 was 97:3.
Subsequently, on the hole injecting layer, Compound HT-1 was vapor deposited to form a first hole transporting layer with a film thickness of 80 nm.
Compound HT-2 was vapor deposited on the hole transporting layer to fora a second hole transporting layer with a film thickness of 10 nm,
Subsequently on the second hole transporting layer: Compound BH-1 (host material B) and Compound BD-1 (dopant material) were vapor co-deposited to form a light emitting layer with a film thickness of 25 nm. The mass ratio of Compound BH-1 and Compound BD-1 was 96:4.
Subsequently, on the light emitting layer, Compound Inv-1 was vapor deposited to form a first electron transporting layer with a film thickness of 10 nm.
Compound ET-1 was vapor deposited on the first electron transporting layer to form a second electron transporting layer with a film thickness of 15 nm.
On the second electron transporting layer, Yb was vapor deposited to form an electron injecting electrode with a film thickness of 1 nm.
Finally, on the electron injecting electrode, metal Al was vapor deposited to form a metal cathode with a film thickness of 80 nm.
The layer configuration of the organic EL device of Example 1 is shown as follows. The numeral in parentheses indicates the film thickness (nm), and the ratio is a mass ratio.
ITO (130)/(HT-1:HI-1=97:3) (10)/HT-1 (80)/HT-2 (10)/(BH-1:BD-1=96:4 (25)/Compound Inv-1 (10)/ET-1 (15)/Yb (1)/Al (80)
Similar to Example 1, the cleaned glass substrate provided with a transparent electrode was mounted on a substrate holder of a vacuum vapor deposition apparatus, and firstly, Compound HT-3 and Compound HI-1 were vapor co-deposited on a surface having the transparent electrode formed thereon, so as to cover the transparent electrode, resulting in a hole injecting layer with a film thickness of 10 nm. The mass ratio of Compound HT-3 and Compound HI-1 was 97:3.
Subsequently, on the hole injecting layer, Compound HT-3 was vapor deposited to form a first hole transporting layer with a film thickness of 80 nm.
Compound HT-2 was vapor deposited on the hole transporting layer to form a second hole transporting layer with a film thickness of 5 nm.
Subsequently, on the second hole transporting layer, Compound BH-2 (host material B) and Compound BD-1 (dopant material) were vapor co-deposited to form a light emitting layer with a film thickness of 25 nm. The mass ratio of Compound BH-2 and Compound BD-1 was 96:4.
Subsequently, on the light emitting layer, Compound Inv-1 was vapor deposited to form a first electron transporting layer with a film thickness of 5 nm.
Compound ET-2 and Liq were vapor co-deposited on the first electron transporting layer to form a second electron transporting layer with a film thickness of 20 nm. The mass ratio of Compound ET-2 to Liq was 50:50.
On the second electron transporting layer, Yb was vapor deposited to form an electron injecting electrode with a film thickness of 1 nm.
Finally, on the electron injecting electrode, metal Al was vapor deposited to form a metal cathode with a film thickness of 50 nm.
The layer configuration of the organic EL device of Example 22 is shown as follows. The numeral in parentheses indicates the film thickness (nm), and the ratio is a mass ratio.
ITO (130)/(HT-3:HI-1=97:3) (10)/HT-3 (80)/HT-2 (5)/(BH-2:BD-1=96:4 (25)/Compound Inv-1 (5)/ET-2:Liq=50:50 (20)/Yb (1)/Al (50)
The resulting organic EL device was driven with a direct constant current at a current density of 50 mA/cm2, and the period of time until the luminance was reduced to 95% of the initial luminance was measured and was defined as LT95 (95% lifetime). The results are shown in Table 1.
Each organic EL device was produced in the same manner as in Example 1 except that Compound Inv-2 (Example 2), Compound Inv-3 (Example 3), Compound Inv-4 (Example 4), Compound Inv-5 (Example 5), Compound Inv-6 (Example 6), Compound Inv-7 (Example 7), Compound Inv-8 (Example 8), Compound Inv-9 (Example 9), Compound Inv-10 (Example 10), Compound Inv-11 (Example 11), Compound Inv-12 (Example 12), Compound Inv-13 (Example 13), Compound Inv-14 (Example 14), Compound Inv-15 (Example 15), Compound Inv-16 (Example 16), Compound Inv-17 (Example 17), Compound Inv-18 (Example 18), Compound Inv-19 (Example 19), Compound Inv-20 (Example 20), Compound Inv-21 (Example 21), or Comparative Compound Ref-1 (Comparative Example 1) was used instead of Compound Inv-1 in Example 1.
The 95% lifetime (LT95) of each of the resulting organic EL devices was obtained in the same manner as in Example 1. The results are shown in Table 1.
Each organic EL device was produced in the same manner as in Example 22 except that Compound Inv-2 (Example 23), Compound Inv-3 (Example 24), Compound Inv-5 (Example 25), Compound Inv-6 (Example 26), Compound Inv-8 (Example 27), Compound Inv-9 (Example 28), Compound Inv-10 (Example 29), Compound Inv-11 (Example 30), Compound Inv-12 (Example 31), Compound Inv-13 (Example 32), Compound Inv-14 (Example 33), Compound Inv-15 (Example 34), Compound Inv-17 (Example 35), Compound Inv-18 (Example 36), Compound Inv-20 (Example 37), Compound Inv-21 (Example 38), or Comparative Compound Ref-1 (Comparative Example 2) was used instead of Compound Inv-1 in Example 22.
The 95% lifetime (LT95) of each of the resulting organic EL devices was obtained in the same manner as in Example 22. The results are shown in Table 2.
It can be seen from the results in Table 1 that compared to the organic EL device of Comparative Example 1 in which the first electron transporting layer contains Comparative Compound Ref-1, the organic EL devices of Examples 1 to 21 in which the first electron transporting layer contains each of Compounds Inv-1 to Inv-21 have a longer life.
It can be seen from the results in Table 2 (other compounds used in the production of the organic EL device, including the change of the host material B, are partially different; however, they are all fixed in each Example and Comparative Example) that compared to the organic EL device of Comparative Example 2 in which the first electron transporting layer contains Comparative Compound Ref-1, the organic EL devices of Examples 22 to 38 in which the first electron transporting layer contains each of Compounds Inv-1 to Inv-3, Inve-5, Inv-6, Inv-8 to Inv-15, Inv-17, Inv-18, Inv-20, and Inv-21 have a longer life.
4-bromo-1-naphthoaldehyde (9.0 g), acetophenone (4.6 g) and sodium hydroxide (0.15 g) were added to 300 mL of ethanol and stirred at room temperature for 5 hours. Then, benzamidine hydrochloride (6.0 g) and sodium hydroxide (1.8 g) were added, and the mixture was stirred at 70° C. for 5 hours. After completion of the reaction, the precipitate was separated by filtration and purified by silica gel column chromatography (developing solvent; hexane/toluene) to obtain Intermediate A as a white solid (7.6 g, yield 45%).
Intermediate A (3.6 g) and 4-(9H-carbazole-9-yl) phenylboronic acid (2.8 g) were added to 1,2-dimethoxyethane (80 mL), and argon gas was passed through the solution for 5 minutes. Pd (PPh3)4 (0.4 g) and a sodium carbonate aqueous solution (2M, 12 mL) were added to the solution, and the mixture was heated under reflux conditions for 7 hours while stirring in an argon atmosphere. The solvent of the reaction solution was distilled off, and the resulting solid was purified by silica gel column chromatography (developing solvent; hexane/toluene) to obtain Compound Inv-1 as a white solid (3.7 g, yield 75%).
The result of mass spectrum analysis revealed m/e=600 with respect to a molecular weight of 599.74, from which the compound was identified as Compound Inv-1.
Compound Inv-2 was obtained as a white solid (6.6 g. yield 85%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate A (5.0 g) and [4′-(carbazole-9-yl)-4-biphenylyl] boronic acid (4.5 g) were used.
The result of mass spectrum analysis revealed m/e=676 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-2.
4-bromo-1-naphthaldehyde (8.0 g), 4-acetylbiphenyi (7.0 g) and sodium hydroxide (0.27 g) were added to 600 m of ethanol and stirred at room temperature for 5 hours. Then, benzamidine hydrochloride (8.0 g) and sodium hydroxide (2.7 g) were added, and the mixture was stirred at 70° C. for 5 hours. After completion of the reaction, the precipitate was separated by filtration and purified by silica gel column chromatography (developing solvent; hexane/toluene) to obtain intermediate B as a white solid (5.0 g, yield 28%).
Compound Inv-3 was obtained as a white solid (4.5 g. yield 68%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate B (5.0 g) was used.
The result of mass spectrum analysis revealed m/e=676 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-3.
Intermediate C was obtained as a white solid (9.0 g, yield 83%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate A (10.0 g) and 4-fluorophenylboronic acid (3.5 g) were used.
Intermediate C (3.8 g), 3,6-diphenylcarbazole (4.0 g) and cesium carbonate (8.2 g) were added to 30 m L of N-methylpyrrolidone (NMP) and stirred at 160° C. for 24 hours. After the reaction solution was cooled to room temperature, 100 mL of methanol and 100 mL of water were added and the mixture was stirred at room temperature for 1 hour. The precipitated solid was collected by filtration and purified by silica gel column chromatography (developing solvent; hexane/toluene) to obtain Compound Inv-4 as a white solid (6.3 g, yield 94%).
The result of mass spectrum analysis revealed m/e=752 with respect to a molecular weight of 751.93, from which the compound was identified as Compound
Intermediate D was obtained as a white solid (4.2 g yield 78%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate A (5.0 g) and 3,5-difluorophenylboronic acid (2.0 g) were used.
Compound Inv-5 was obtained as a white solid (4.1 g, yield 60%) under the same conditions as in (4-2) of Synthesis Example 4 except that Intermediate D (4.2 g) and carbazole (4.5 g) were used.
The result of mass spectrum analysis revealed m/e=765 with respect to a molecular weight of 764.93, from which the compound was identified as Compound Inv-5.
Compound Inv-6 was obtained as a white solid (4.7 g, yield 78%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate A (3.9 g) and 9-phenyl-3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-9H-carbazole (4.0 g) were used.
The result of mass spectrum analysis revealed m/e=676 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-6.
Compound Inv-7 was Obtained as a white solid (7.0 g yield 73%) under the same conditions as in (1-2) of Synthesis Example 1 except that Intermediate A (7.0 g) and 3-(9H-carbazole-9-yl) phenylboronic acid (5.1 g) were used,
The result of mass spectrum analysis revealed m/e=600 with respect to a molecular weight of 599.74, from which the compound was identified as Compound Inv-7.
Intermediate A (6.0 g), 3,6-diphenylcarbazole (4.2 g), palladium acetate (0.48 g), Amphos (1.3 g), and t-BuONa (3.8 g) were added to 168 mL of dehydrated xylene and stirred under reflux conditions for 36 hours. After the reaction solution was cooled to room temperature, 100 mL of methanol and 100 mL of water were added and the mixture was stirred at room temperature for 1 hour. The precipitated solid was collected by filtration and purified by silica gel column chromatography (developing solvent:hexane/toluene) to obtain Compound Inv-8 as a white solid (4.8 g, yield 52%).
The result of mass spectrum analysis revealed m/c=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound nv-8.
Compound Inv-9 was obtained as a white solid (5.9 g, yield 61%) under the same conditions as those described in (4-2) of Synthesis Example 4 using Intermediate C (5.6 g).
The result of mass spectrum analysis revealed m/e=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound
Compound Inv-10 was obtained as a white solid (10.3 g, yield 87%) under the same conditions as those described in Synthesis Example 1 using Intermediate E (8.0 g), which was synthesized according to the method in (3-1) of Synthesis Example 3 using 3-acetylbiphenyl as a starting material.
The result of mass spectrum analysis revealed m/e=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-10.
Compound Inv-11 was obtained as a white solid (5.7 g, yield 78%) under the same conditions as those described in Synthesis Example 1 using Intermediate E (5.0 g) and Intermediate F (3.6 g).
The result of mass spectrum analysis revealed m/e=751 with respect to a molecular weight of 751.93, from which the compound was identified as Compound Inv-11.
Compound Inv-12 was obtained as a white solid (5.1 g, yield 87%) under the same conditions as those described in Synthesis Example 1 using Intermediate B (4.0 g) and Intermediate F (2.8 g).
The result of mass spectrum analysis revealed m/e=751 with respect to a molecular weight of 751.93, from which the compound was identified as Compound Inv-12.
Intermediate G was obtained as a white solid (9.8 g, yield 91%) under the same conditions as those described in Synthesis Example 1 using Intermediate A (10.0 g) and 4-chlorophenylboronic acid (3.6 g).
Intermediate G (4.5 g), N-phenylcarbazole-2-boronic acid (4.1 g), and tripotassium phosphate (8.2 g) were added to 1,4-dioxane (100 mL), and argon gas was passed through the solution for 5 minutes. Pd2(dba)3 (0.18 g) and SPhos (0.82 g) were added to the solution, and the mixture was heated under reflux conditions for 24 hours while stirring in an argon atmosphere. The solvent of the reaction solution was distilled off, and the resulting solid was purified by silica gel column chromatography (developing solvent; hexane/toluene) to obtain Compound Inv-13 as a white solid (5.8 g, yield 90%).
The result of mass spectrum analysis revealed m/e=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-13.
Compound Inv-14 was obtained as a white solid (3.1 g, yield 62%) under, the same conditions as those described in (13-2) of Synthesis Example 13 using Intermediate G (3.5 g) and N-phenylcarbazole-4-boronic acid (3.2 g).
The result of mass spectrum analysis revealed m/e 675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-14.
Intermediate H was obtained as a white solid (4.3 g, yield 80%) under the same conditions as those described in Synthesis Example 1 using Intermediate A (5.0 g) and 3,4-difluorophenylboronic acid (2.5 g).
Inv-15 was obtained as a white solid (5.5 g, yield 79%) under the same conditions as those described in Synthesis Example 3 using Intermediate H (4.3 g).
The result of mass spectrum analysis revealed m/e=764 with respect to a molecular weight of 764.93, from which the compound was identified as Compound Inv-15.
Intermediate I was obtained as a white solid (4.8 g, yield 92%) under the same conditions as those described in Synthesis Example 1 using Intermediate A (5.0 g) and 3-fluorophenylboronic acid (2.2 g).
Compound Inv-16 was obtained as a white solid (7.2 g, yield 90%) under the same conditions as those described in Synthesis Example 3 using Intermediate I (4.8 g) and 3,6-diphenylcarbazole (5.0 g).
The result of mass spectrum analysis revealed m/e=751 with respect to a molecular weight of 751.93, from which the compound was identified as Compound. Inv-16.
Compound Inv-17 was obtained as a white solid (5.0 g, yield 76%) under the same conditions as those described in Synthesis Example 1 using Intermediate B (4.0 g) and [4′-(carbazole-9-yl)-4-biphenylyl]boronic acid (3.4 g).
The result of mass spectrum analysis revealed m/e=751 with respect to a molecular weight of 751.93, from which the compound was identified as Compound. Inv-17.
Compound Inv-18 was obtained as a white solid (5.5 g, yield 92%) under the same conditions as those described in Synthesis Example 1 using Intermediate B (4.5 g) and N-phenylcarbazole-4-boronic acid (3.0 g).
The result of mass spectrum analysis revealed m/e=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound Inv-18.
Compound Inv-19 was obtained as a white solid (5.6 g, yield. 85%) under the same conditions as those described in Synthesis Example 1 using Intermediate B (5.0 g) and 3-(N-carbazole)phenylboronic acid (3.4 g).
The result of mass spectrum analysis revealed m/e=675 with respect to a molecular weight of 675.84, from which the compound was identified as Compound
Intermediate J was obtained as a white solid (4.5 g, yield 87%) under the same conditions as those described in Synthesis Example 1 using Intermediate B (5.0 g) and 4-fluorophenylboronic acid (1.6 g).
Compound Inv-20 was obtained as a white solid (3.8 g, yield 65%) under the same conditions as those described in Synthesis Example 3 using Intermediate J (4.5 g) and carbazole-d8 (2.2 g),
The result of mass spectrum analysis revealed m/e=683 with respect to a molecular weight of 683.88, from which the compound was identified as Compound Inv-20.
Intermediate K was obtained as a white solid (5.1 g, yield 30%) according to the method of synthesizing Intermediate A using acetophenone (phenyl-d5) (4.8 g) instead of acetophenone.
Compound Inv-21 was obtained as a white solid 12.0 g, yield 43%) under the same conditions as those described in Synthesis Example 1 using Intermediate K (3.0 g) and [4′-(carbazole-9-yl)-4-biphenylyl]boronic acid (2.5 g).
The result of mass spectrum analysis revealed m/e=680 with respect to a molecular weight of 680.87, from which the compound was identified as Compound Inv-21.
In addition, the compound of the present invention can also be synthesized via the following synthetic intermediates according to the conditions described in the synthesis examples respectively.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-018229 | Feb 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/004020 | 2/4/2021 | WO |
