Patent Application
20200231580
The present invention relate to a novel organic compound and an organic electroluminescent device including the same, and in particular, to a novel dibenzofuran-based compound having excellent thermal stability, carrier transport ability, light emitting ability and the like, and an organic electroluminescent device having low driving voltage, and enhanced luminous efficiency, lifetime properties and the like by including the novel dibenzofuran-based compound as a material of one or more organic material layers.
With the observation of organic thin film light emission made by Bemanose in 1950s as a start, studies on organic electroluminescent (EL) devices (hereinafter, simply referred to as ‘organic EL device’) leading to blue electroluminescence using a single anthracene crystal in 1965 have been continued, and in 1987, an organic EL device having a two-layer laminated structure formed with a hole layer (NPB) and a light emitting layer (Alq3) has been proposed by Tang.
After that, in order for an organic EL device to obtain properties of high efficiency and long lifetime required for commercialization, a form of a multilayer laminated structure providing each of distinguishing and subdivided functions such as an organic layer responsible for hole injection and transfer, an organic layer responsible for electron injection and transfer, an organic layer inducing electroluminescence by bonding holes and electrons, and the like in the device has been proposed.
When a voltage is applied between the two electrodes in an organic electroluminescent device, holes and electrons are injected to an organic material layer from the anode and the cathode, respectively. When the injected holes and electrons meet, excitons are formed, and light emits when these excitons fall back to the ground state. Materials included in the organic material layer may be divided into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like depending on the function.
As for an electron spin of excitons formed by recombination of electrons and holes, singlet excitons and triplet excitons are produced in a ratio of 25% and 75%, respectively. Herein, depending on the electron spin type of formed excitons, an organic EL device may be divided into a fluorescent EL device in which singlet excitons contribute to light emission, and a phosphorescent EL device in which triplet excitons contribute to light emission.
In the fluorescent EL device having light emission by singlet excitons, internal quantum efficiency may not theoretically exceed 25% by the ratio of generation, and external quantum efficiency is accepted to have a limit of 5%.
In the phosphorescent EL device having light emission by triplet excitons, luminous efficiency may be enhanced by up to 4 times compared to fluorescence when using a metal complex compound including a transition metal heavy atom such as Ir or Pt as a phosphorescent dopant.
As described above, the phosphorescent EL device theoretically exhibits higher efficiency than fluorescence in terms of luminous efficiency. However, unlike green and red phosphorescent devices, a blue phosphorescent device has not been commercialized due to insignificant development levels for color purity of deep blue color, highly efficient phosphorescent dopant, and a host with a wide energy gap, and blue fluorescent device products have been used instead.
As performance of an organic EL device has been enhanced to a commercializable level by introducing a multilayer laminated structure, there have been attempts to expand its application to, beginning with radio display products for vehicles in 1997, portable information display devices and display devices for TV.
In addition, with a recent trend toward large and high resolution displays, development of an organic EL device having high efficiency and long lifetime has been required. Particularly, high resolution of a display is obtained when more pixels are formed in the same area. The organic EL pixels have a reduced light emitting area by such high resolution, which eventually shortens a lifetime, and this has become the most important challenge that an organic EL device needs to overcome.
However, existing organic EL device materials have a low glass transition temperature and thereby have decreased thermal stability, and a satisfactory level has not been obtained in terms of a lifetime of an organic electroluminescent device and an improvement has also been required in terms of light emission properties.
The present invention is directed to providing a novel compound capable of being used as a light emitting layer material, a hole transport layer material, a light emitting auxiliary layer material, a hole blocking layer material or the like by having excellent thermal stability, carrier transport ability, light emitting ability and the like.
The present invention is also directed to providing an organic electroluminescent device having low driving voltage, high luminous efficiency, and enhanced lifetime properties by including the novel compound.
One embodiment of the present invention provides a compound represented by the following Chemical Formula 1:
wherein,
X1 is selected from the group consisting of O, S, C(R9)(R10) and N(R11),
at least one of R1 and R2, R2 and R3, R3 and R4, R4 and R5, R5 and R6, R6 and R7, and R7 and R8 is fused with the ring represented by Chemical Formula 2 to form a fused ring,
R1, R2, R3, R4, R5, R6, R7 and R8 not forming a fused ring with the ring represented by Chemical Formula 2 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group, or may bond to adjacent groups to form a fused ring,
a dotted line of Chemical Formula 2 is a part fused to Chemical Formula 1,
X2 and X3 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C2 alkyl group and a C6˜C60 aryl group,
L is selected from the group consisting of a single bond, a C6˜C18 arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
R9 to R11 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group,
R12 is selected from the group consisting of a C6˜C60 acyl group, a heteroaryl group having 5 to 60 nuclear atoms, a C3˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 mono or diarylphosphinyl group and a C6˜C60 arylamine group, and
the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the heterocycloalkyl group, the aryl group, the heteroaryl group, the alkyloxy group, the aryloxy group, the alkylsilyl group, the arylsilyl group, the alkylboron group, the arylboron group, the arylphosphine group, the arylphosphine oxide group, the mono or diarylphosphinyl group and the arylamine group of R1 to R12, X2 and X3 are each independently unsubstituted or substituted with one or more types of substituents selected from the group consisting of a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C3˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 mono or diarylphosphinyl group and a C6˜C60 arylamine group, and when substituted with a plurality of the substituents, these may be the same as or different from each other.
Another embodiment of the present invention provides an organic electroluminescent device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein at least one of the one or more organic material layers includes the compound of Chemical Formula 1.
The “alkyl” in the present invention means a monovalent substituent derived from linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof may include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl and the like, but are not limited thereto.
The “alkenyl” in the present invention means a monovalent substituent derived from linear or branched unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 40 carbon atoms. Examples thereof may include vinyl, allyl, isopropenyl, 2-butenyl and the like, but are not limited thereto.
The “alkynyl” in the present invention means a monovalent substituent derived from linear or branched unsaturated hydrocarbon having one or more carbon-carbon triple bonds and having 2 to 40 carbon atoms. Examples thereof may include ethynyl, 2-propynyl and the like, but are not limited thereto.
The “aryl” in the present invention means a monovalent substituent derived from aromatic hydrocarbon having a single ring or two or more rings combined and having 6 to 60 carbon atoms. In addition, a form of two or more rings simply attached (pendant) or fused with each other may also be included. Examples of such awl may include phenyl, naphthyl, phenanthryl, anthryl and the like, but are not limited thereto.
The “heteroaryl” in the present invention means a monovalent substituent derived from monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. Herein, one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O, S or Se. In addition, a form of two or more rings simply attached (pendant) or fused with each other may also be included, and furthermore, a form fused with an aryl group may also be included. Examples of such heteroaryl may include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl or triazinyl, polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole or carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.
The “aryloxy” in the present invention is a monovalent substituent represented by RO-, and R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy may include phenyloxy, naphthyloxy, diphenyloxy and the like, but are not limited thereto.
The “alkyloxy” in the present invention is a monovalent substituent represented by R′O-, and R′ means alkyl having 1 to 40 carbon atoms and may include a linear, branched or cyclic structure. Examples of the alkyloxy may include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like, but are not limited thereto.
The “arylamine” in the present invention means amine substituted with aryl having 6 to 60 carbon atoms.
The “cycloalkyl” in the present invention means a monovalent substituent derived from monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl may include cyclopropyl, cyclopentyl, cyclohexyl, norbomyl, adamantine and the like, but are not limited thereto.
The “heterocycloalkyl” in the present invention means a monovalent substituent derived from non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and one or more carbons, preferably 1 to 3 carbons, in the ring are substituted with a heteroatom such as N, O, S or Se. Examples of such heterocycloalkyl may include morpholine, piperazine and the like, but are not limited thereto.
The “alkylsilyl” in the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, and the “arylsilyl” means silyl substituted with aryl having 6 to 60 carbon atoms.
The “fused ring” in the present invention means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combined form thereof.
A compound provided in the present invention has excellent thermal stability, carrier transport ability, light emitting ability and the like, and therefore, is useful as an organic material layer material of an organic electroluminescent device.
In addition, an organic electroluminescent device including the compound of the present invention in an organic material layer has properties of excellent light emitting performance, low driving voltage, high efficiency and long lifetime, and can be effectively used in a full color display panel and the like.
Hereinafter, the present invention will be described.
1. Novel Organic Compound
One embodiment of the present invention provides a novel compound having excellent thermal stability, carrier transport ability, light emitting ability and the like.
Specifically, the novel organic compound according to the present invention has a structure in which an indene moiety or the like is fused to a hetero compound to form a basic skeleton, and various substituents bond or are fused to such a basic skeleton.
Preferably, the novel organic compound of the present invention may be represented by the following Chemical Formula 1:
wherein,
X1 is selected from the group consisting of O, S, C(R9)(R10) and N(R11),
at least one of R1 and R2, R2 and R3, R3 and R4, R4 and R5, R5 and R6, R6 and R7, and R7 and R8 is fused with the ring represented by Chemical Formula 2 to form a fused ring,
R1, R2, R3, R4, R5, R6, R7 and R8 not forming a fused ring with the ring represented by Chemical Formula 2 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group, or may bond to adjacent groups to form a fused ring,
a dotted line of Chemical Formula 2 is a part fused to Chemical Formula 1,
X2 and X3 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C2 alkyl group and a C6˜C60 aryl group,
L is selected from the group consisting of a single bond, a C6˜C18 arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
R9 to R11 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group,
R12 is selected from the group consisting of a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 mono or diarylphosphinyl group and a C6˜C60 arylamine group, and
the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the heterocycloalkyl group, the aryl group, the heteroaryl group, the alkyloxy group, the aryloxy group, the alkylsilyl group, the arylsilyl group, the alkylboron group, the arylboron group, the arylphosphine group, the arylphosphine oxide group, the mono or diarylphosphinyl group and the arylamine group of R1 to R12, X2 and X3 are each independently unsubstituted or substituted with one or more types of substituents selected from the group consisting of a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C3˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 mono or diarylphosphinyl group and a C6˜C60 arylamine group, and when substituted with a plurality of the substituents, these may be the same as or different from each other.
More specifically, the novel organic compound according to the present invention has a structure in which an indene moiety or the like is fused to a compound formed with dibenzofuran, dibenzothiophene, fluorene and carbazole to form a basic skeleton, preferably, an indene moiety or the like is fused to dibenzofuran to form a basic skeleton, and various substituents bond or are fused thereto.
According to preferred one embodiment of the present invention, Chemical Formula 1 may be represented by the following Chemical Formulae 3 to 8:
wherein,
X1 to X3, L and R1 to R8 each have the same definition as in Chemical Formula 1.
According to preferred one embodiment of the present invention, X1 of Chemical Formula 1 to Chemical Formula 8 may be O.
According to preferred one embodiment of the present invention, X2 and X3 of Chemical Formula 1 to Chemical Formula 8 may be a methyl group.
According to preferred one embodiment of the present invention, R12 of Chemical Formula 2 may be a substituent represented by any one of the following Chemical Formula 9 to Chemical Formula 11:
wherein,
* means a part forming a bond,
n is an integer of 0 to 2,
Y1 to Y3 are the same as or different from each other and each independently C(R15) or N, and at least one or more are N,
Y4 to Y7 are the same as or different from each other, and each independently C(R16) or N,
X4 is selected from the group consisting of O, S, C(R17)(R18), Si(R19)(R20) and N(R21),
R12 to R14 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C3˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C6˜C60 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group,
R15 and R16 are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a nitro group, a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group, or may bond to adjacent groups to form a fused ring,
R17 to R21 are the same as or different from each other, and each independently selected from the group consisting of a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C1˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 arylphosphine oxide group and a C6˜C60 arylamine group, or may bond to adjacent groups to form a fused ring, and
the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the heterocycloalkyl group, the aryl group, the heteroaryl group, the alkyloxy group, the aryloxy group, the alkylsilyl group, the arylsilyl group, the alkylboron group, the arylboron group, the arylphosphine group, the arylphosphine oxide group, the mono or diarylphosphinyl group and the arylamine group of R12 to R21 are each independently unsubstituted or substituted with one or more types of substituents selected from the group consisting of a C1˜C40 alkyl group, a C2˜C40 alkenyl group, a C2˜C40 alkynyl group, a C3˜C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6˜C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1˜C40 alkyloxy group, a C6˜C60 aryloxy group, a C3˜C40 alkylsilyl group, a C6˜C60 arylsilyl group, a C1˜C40 alkylboron group, a C6˜C60 arylboron group, a C6˜C60 arylphosphine group, a C6˜C60 mono or diarylphosphinyl group and a C6˜C60 arylamine group, and when substituted with a plurality of the substituents, these may be the same as or different from each other.
According to preferred one embodiment of the present invention, L may be a single bond, a phenylene group or a biphenylene group.
According to preferred one embodiment of the present invention, the compound represented by Chemical Formula 1 may be selected from the group consisting of the following compounds.
The compound represented by Chemical Formula 1 is a compound selected from the group consisting of the following compounds:
The compound of Chemical Formula 1 of the present invention may be synthesized using general synthesis methods (refer to Chem. Rev., 60:313 (1960); J. Chem. SOC. 4482 (1955); Chem. Rev. 95: 2457 (1995) or the like). Detailed synthesis processes of the compounds of the present invention will be specifically described in synthesis examples to be described later.
2. Organic Electroluminescent Device
Meanwhile, another aspect of the present invention provides an organic electroluminescent device including the compound represented by Chemical Formula 1.
Specifically, the present invention relates to an organic electroluminescent device including (i) an anode, (ii) a cathode and (iii) one or more organic material layers provided between the anode and the cathode, and at least one of the organic material layers includes the compound represented by Chemical Formula 1. Herein, the compound represented by Chemical Formula 1 may be used either alone or as a mixture of two or more types.
According to one embodiment of the present invention, the one or more organic material layers may include any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, and at least one organic material layer thereof may include the compound represented by Chemical Formula 1.
Preferably, the organic material layer including the compound represented by Chemical Formula 1 may be a light emitting layer or a hole transport layer. More preferably, when the compound represented by Chemical Formula 1 is included in a light emitting layer, luminous efficiency, luminance, power efficiency, thermal stability and device lifetime of an organic electroluminescent device may be significantly enhanced.
For example, the compound represented by Chemical Formula 1 may be a phosphorescent host, a fluorescent host or a dopant material of a light emitting layer, and may be preferably a phosphorescent host of a light emitting layer.
According to another embodiment of the present invention, the one or more organic material layers may include any one or more of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and an electron injection layer, and herein, at least one of the organic material layers may include the compound represented by Chemical Formula 1.
Preferably, the organic material layer including the compound represented by Chemical Formula 1 may be a light emitting auxiliary layer. Particularly, when the compound represented by Chemical Formula 1 is included in a light emitting auxiliary layer material of an organic electroluminescent device, efficiency (luminous efficiency and power efficiency), lifetime and luminance of the organic electroluminescent device may be further enhanced, and driving voltage may be further lowered.
According to another embodiment of the present invention, the one or more organic material layers may include any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and herein, at least one of the organic material layers may include the compound represented by Chemical Formula 1.
Preferably, the organic material layer including the compound represented by Chemical Formula 1 may be a hole blocking layer. Particularly, when the compound represented by Chemical Formula 1 is included in a hole blocking layer of an organic electroluminescent device, efficiency (luminous efficiency and power efficiency), lifetime and luminance of the organic electroluminescent device may be further enhanced, and driving voltage may be further lowered.
The structure of such an organic electroluminescent device of the present invention is not particularly limited, and examples thereof may include a structure of, as well as consecutively laminating an anode, one or more organic material layers and a cathode on a substrate, inserting an insulating layer or an adhesive layer at an interface of the electrode and the organic material layer.
According to one embodiment, the organic electroluminescent device may have a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode are consecutively laminated on a substrate, and as necessary, a light emitting auxiliary layer may be inserted between the hole transport layer and the light emitting layer, and an electron injection layer may also be disposed on the electron transport layer.
The organic electroluminescent device of the present invention may be manufactured by forming organic material layers and electrodes using materials and methods known in the art except that at least one of the one or more organic material layers, for example, a light emitting layer or a light emitting auxiliary layer, is formed to include the compound represented by Chemical Formula 1.
The organic material layer may be formed using a vacuum deposition method or a solution coating method. Examples of the solution coating method may include spin coating, dip coating, doctor blading, inkjet printing, thermal transfer method or the like, but are not limited thereto.
Examples of the substrate capable of being used when manufacturing the organic electroluminescent device in the present invention may include silicon wafers, quartz, glass plates, metal plates, plastic films, sheets and the like, but are not limited thereto.
In addition, examples of the anode material may include metals such as vanadium, chromium, copper, zinc or gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) or indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole and polyaniline; carbon black, or the like, but are not limited thereto.
In addition, examples of the cathode material metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead, or alloys thereof; multilayer-structured materials such as LiF/Al or LiO2/Al, or the like, but are not limited thereto.
In addition, materials used as the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and common materials known in the art may be used without limit.
Hereinafter, the present invention will be described in detail with reference to examples, however, the following examples are for illustrative purposes only, and the present invention is not limited to the following examples.
<Step 1> Synthesis of 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
2-Bromodibenzo[b,d]furan (94 g, 0.38 mol), bis(pinacolato)diboron (115.8 g, 0.46 mol), Pd(dppf)Cl2 (31 g, 0.038 mol) and KOAc (111.9 g, 1.14 mol) were introduced to a flask, then dissolved by introducing 1,4-dioxane (2 L) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain compound 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (73 g, yield 62%).
<Step 2> Synthesis of methyl 5-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate 2-(Dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(22.6 g, 76.9 mmol) obtained in <Step 1>, methyl 2-bromo-5-chlorobenzoate (21.1 g, 84.57 mmol) and Pd(PPh3)4 (0.89 g, 0.769 mmol) were introduced to a flask and dissolved in 1,4-dioxane (257 mL) under the nitrogen atmosphere. An aqueous solution (128 ml) having K2CO3 (17 g, 115.3 mmol) dissolved therein was added thereto, and the result was stirred under reflux for 7 hours at 70° C. After the reaction was finished, the result was extracted with ethyl acetate, and then the obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain compound methyl 5-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate (21.8 g, yield 84%).
<Step 3> Synthesis of Compounds Inv 1 and Inv 2
Under the nitrogen atmosphere, methyl 5-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate (21.8 g 64.95 mmol) obtained in <Step 2> was introduced to a three-neck round bottom flask heated and dried under vacuum, then dissolved by adding THF (325 mL) thereto, and the result is was cooled to −10° C. and stirred. 3.0 M CH3MgBr (54 mL) (in ether, 162.4 mmol) was slowly added thereto over 30 minutes. The reaction solution was warmed to room temperature, and stirred for 12 hours under the nitrogen atmosphere. The reaction solution was cooled to 0° C., and then an aqueous solution dissolving NH4Cl (10.4 g, 194.85 mmol) in distilled water (100 mL) was slowly added thereto. The reaction solution was extracted with distilled water and ether, the organic layer solution was dried with Na2SO4 and filtered, and the filtrate was vacuum concentrated. The dried residue was introduced to a three-neck round bottom flask and dissolved by adding CH2C2 (325 mL) thereto under the nitrogen atmosphere, and the result was cooled to 0° C. and stirred. Boron trifluoride dimethyl etherate (4 mL, 32.5 mmol) was slowly added thereto for 10 minutes, and after raising the temperature to room temperature, the result was stirred for 12 hours. When the reaction was finished, an aqueous sodium bicarbonate solution was slowly added thereto at 0° C., and the result was stirred for 30 minutes. The extract obtained by extracting the reaction solution with dichloromethane/distilled water was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain Compound Inv 1 (10.3 g, yield 50%) and Compound Inv 2 (9.3 g, yield 45%).
<Step 1> Synthesis of 2-(dibenzol[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
2-Bromodibenzo[b,d]furan (94 g, 0.38 mol), bis(pinacolato)diboron (115.8 g, 0.46 mol), Pd(dppf)C2 (31 g, 0.038 mol) and KOAc(111.9 g 1.14 mol) were introduced to a flask, then dissolved by introducing 1,4-dioxane (2 L) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain compound 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (73 g, yield 62%).
<Step 2> Synthesis of methyl 4-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate
2-(Dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (69 g, 0.235 mol) obtained in <Step 1>, 2-bromo-4-chloro-1-nitrobenzene (67 g, 0.282 mol) and Pd(PPh3)4 (13.5 g, 0.011 mol) were introduced to a flask and dissolved by introducing a saturated aqueous 2 M Na2CO3 solution (352 ml) and 1,4-dioxane (2 L) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain compound methyl 4-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate (71 g yield 91%).
<Step 3> Synthesis of Compounds Inv 3 and Inv 4
Under the nitrogen atmosphere, methyl 4-chloro-2-(dibenzo[b,d]furan-2-yl)benzoate (21.8 g 64.95 mmol) obtained in <Step 2> was introduced to a three-neck round bottom flask heated and dried under vacuum, then dissolved by adding THF (325 mL) thereto, and the result was cooled to −10° C. and stirred. 3.0 M CH3MgBr (54 mL) (in ether, 162.4 mmol) was slowly added thereto over 30 minutes. The reaction solution was warmed to room temperature, and stirred for 12 hours under the nitrogen atmosphere. The reaction solution was cooled to 0° C., and then an aqueous solution dissolving NH4Cl (10.4 g, 194.85 mmol) in distilled water (100 mL) was slowly added thereto. The reaction solution was extracted with distilled water and ether, the organic layer solution was dried with Na2SO4 and filtered, and the filtrate was vacuum concentrated. The dried residue was introduced to a three-neck round bottom flask and dissolved by adding CH2C2 (325 mL) thereto under the nitrogen atmosphere, and the result was cooled to 0° C. and stirred. Boron trifluoride dimethyl etherate (4 mL, 32.5 mmol) was slowly added thereto for 10 minutes, and after raising the temperature to room temperature, the result was stirred for 12 hours. When the reaction was finished, an aqueous sodium bicarbonate solution was slowly added thereto at 0° C., and the result was stirred for 30 minutes. The extract obtained by extracting the reaction solution with dichloromethane/distilled water was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain Compound Inv 3 (9.3 g, yield 45%) and Compound Inv 4 (8.2 g, yield 39%).
Compound Inv 5 (9.0 g, yield 43%) and Compound Inv 6 (8.6 g, yield 41%) were obtained in the same manner as in Preparation Example 1 except that, in <Step 1>, 3-bromodibenzo[b,d]furan was used instead of 2-bromodibenzo[b,d]furan.
Compound Inv 7 (8.8 g, yield 43%) and Compound Inv 8 (8.9 g, yield 43%) were obtained in the same manner as in Preparation Example 2 except that, in <Step 1>, 3-bromodibenzo[b,d]furan was used instead of 2-bromodibenzo[b,d]furan.
<Step 1> Synthesis of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
Inv 1 (100 g, 0.313 mol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (95.6 g, 0.376 mol), Pd(OAc)2 (7 g, 0.031 mol), X-Phos (14.9 g, 0.031 mol) and KOAc (61.4 g, 0.626 mol) were introduced to a flask, then dissolved by introducing 1,4-dioxane (2 L) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain compound 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (91.1 g, yield 71%).
<Step 2> Synthesis of Cpd 10
2-(7,7-Dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.2 g, 20 mmol) obtained in <Step 1>, 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (8.2 g, 24 mmol), Pd(OAc)2 (0.45 g, 2 mmol), X-Phos (0.95 g 2 mmol) and Cs2CO3 (13.0 g, 40 mmol) were introduced to a flask, then dissolved by introducing 1,4-dioxane (2 L) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain Compound Cpd 10 (9.3 g, yield 79%). HRMS M+: 591.231
Compound Cpd 15 (8.7 g, yield 74%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS[M]+: 591.231
Compound Cpd 16 (9.5 g, yield 71%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-([1,1′-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS [M]+: 667.262
Compound Cpd 18 (10.3 g, yield 76%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-(3-chlorophenyl)-4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS [M]+: 681.242
Compound Cpd 28 (9.7 g, yield 73%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-(4′-chloro-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS[M]+: 667.262
Compound Cpd 29 (10.1 g, yield 76%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-(3′-chloro-[1,1′-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS[M]+: 667.262
Compound Cpd 30 (9.5 g, yield 71%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 2>, 2-(3′-chloro-[1,1′-biphenyl]-4-yl)-4,6-diphenyl-1,3,5-triazine was used instead of 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. HRMS[M]+: 667.262
Compound Cpd 40 (9.1 g, yield 77%) was obtained in the same manner as in
Synthesis Example 1 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 45 (8.6 g, yield 73%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 46 (9.5 g, yield 71%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 48 (9.8 g, yield 72%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 58 (10.0 g, yield 75%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 59 (9.7 g, yield 73%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 60 (10.1 g, yield 76%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 3 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 130 (8.3 g, yield 70%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 135 (9.0 g, yield 76%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 136 (10.3 g, yield 77%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 138 (10.2 g, yield 75%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 148 (9.6 g, yield 72%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 149 (9.7 g, yield 73%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 150 (9.6 g, yield 72%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 6 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 160 (9.1 g, yield 77%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 165 (8.6 g, yield 73%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 166 (9.5 g, yield 71%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 168 (9.8 g, yield 72%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 178 (10.0 g, yield 75%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 179 (9.7 g, yield 73%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 180 (10.1 g, yield 76%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 8 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 190 (8.8 g, yield 74%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 195 (9.2 g, yield 78%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 196 (10.0 g, yield 75%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 198 (10.4 g, yield 76%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 208 (10.2 g, yield 76%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 209 (9.5 g, yield 71%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 210 (9.9 g, yield 74%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 2 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 220 (9.2 g, yield 78%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 225 (9.3 g, yield 79%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 226 (9.8 g, yield 73%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 228 (10.4 g, yield 76%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 238 (10.3 g, yield 77%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 239 (9.9 g, yield 74%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 240 (10.4 g, yield 78%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 4 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 310 (8.5 g, yield 72%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 315 (8.9 g, yield 75%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 316 (10.2 g, yield 76%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 318 (10.4 g, yield 76%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 328 (10.3 g, yield 77%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 329 (9.9 g, yield 74%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 330 (10.0 g, yield 75%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 5 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 340 (9.3 g, yield 79%) was obtained in the same manner as in Synthesis Example 1 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 345 (9.0 g, yield 76%) was obtained in the same manner as in Synthesis Example 2 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 591.231
Compound Cpd 346 (10.4 g, yield 78%) was obtained in the same manner as in Synthesis Example 3 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 348 (10.2 g, yield 75%) was obtained in the same manner as in Synthesis Example 4 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 681.242
Compound Cpd 358 (9.9 g, yield 74%) was obtained in the same manner as in Synthesis Example 5 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 359 (9.6 g, yield 72%) was obtained in the same manner as in Synthesis Example 6 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 667.262
Compound Cpd 360 (10.0 g, yield 75%) was obtained in the same manner as in Synthesis Example 7 except that, in <Step 1>, Inv 7 was used instead of Inv 1. HRMS[M]+: 667.262
2-(7,7-Dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.2 g 20 mmol) obtained in Synthesis Example 1, 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole (11.4 g, 24 mmol) and Pd(PPh3)4 (1.2 g, 1 mmol) were introduced to a flask and dissolved by introducing a saturated aqueous 2 M Na2CO3 solution (30 ml) and 1,4-dioxane (100 ml) thereto, and the result was stirred for 8 hours while heating. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain Compound Cpd 363 (11.3, yield 83%). HRMS[M]+: 680.258
Compound Cpd 367 (12.8 g, yield 85%) was obtained in the same manner as in Synthesis Example 57 except that 9-(4-([1,1′-biphenyl]-4-yl)-6-phenyl-1,3,5-triazin-2-yl)-3-bromo-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 756.289
Compound Cpd 370 (12.3 g, yield 80%) was obtained in the same manner as in Synthesis Example 57 except that 3-bromo-9-(4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 770.268
Compound Cpd 371 (12.6 g, yield 82%) was obtained in the same manner as in Synthesis Example 57 except that 3-bromo-9-(4-(dibenzo[b,d]furan-2-yl)-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 770.268
Compound Cpd 409 (9.4 g, yield 72%) was obtained in the same manner as in Synthesis Example 57 except that 3-bromo-9-(4-phenylquinazolin-2-yl)-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 653.247
Compound Cpd 411 (10.8 g, yield 74%) was obtained in the same manner as in Synthesis Example 57 except that 3-bromo-9-(4-(4-phenylquinazolin-2-yl)phenyl)-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 729.278
Compound Cpd 412 (10.3 g, yield 71%) was obtained in the same manner as in Synthesis Example 57 except that 3-bromo-9-(3-(4-phenylquinazolin-2-yl)phenyl)-9H-carbazole was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 729.278
Compound Cpd 413 (9.8 g, yield 75%) was obtained in the same manner as in Synthesis Example 61 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 653.247
Compound Cpd 415 (10.3 g, yield 71%) was obtained in the same manner as in Synthesis Example 62 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 729.278
Compound Cpd 416 (10.5 g, yield 72%) was obtained in the same manner as in Synthesis Example 63 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 729.278
Compound Cpd 417 (10.0 g, yield 87%) was obtained in the same manner as in Synthesis Example 57 except that N-(4-bromophenyl)-N-phenylnaphthalen-1-amine was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 577.241
Compound Cpd 418 (12.1 g, yield 89%) was obtained in the same manner as in Synthesis Example 57 except that N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)[1,1′-biphenyl]-4-amine was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 679.288
Compound Cpd 420 (12.5 g, yield 87%) was obtained in the same manner as in Synthesis Example 57 except that N-([1,1′-biphenyl]-4-yl)-N-(4-bromophenyl)-9,9-dimethyl-9H-fluoren-2-amine was used instead of 3-bromo-9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazole. HRMS[M]+: 719.319
After dissolving Compound Inv 1 (6.4 g, 20.0 mmol) synthesized in Preparation Example 1 and di([1,1′-biphenyl]-4-yl)amine (7.7 g, 24.0 mmol) in toluene (100 ml), Pd2(dba)3 (0.9 g, 1.0 mmol) was introduced thereto under nitrogen. After that, NaOtBu (38.4 g, 40 mmol) was introduced thereto, and after introducing (t-Bu)3P (1.0 ml, 1.0 mmol) to the reaction solution, the mixture was stirred for 5 hours under reflux.
After identifying termination of the reaction by TLC, the result was cooled to room temperature. After the reaction was finished, distilled water was introduced thereto, and the organic layer was extracted with ethyl acetate. The obtained organic layer was dried with Na2SO4, vacuum distilled, and then purified using column chromatography to obtain Compound Cpd 419 (10.7 g, yield 89%). HRMS[M]+: 603.256
Compound Cpd 429 (10.1 g, yield 88%) was obtained in the same manner as in Synthesis Example 67 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 577.241
Compound Cpd 430 (11.4 g, yield 84%) was obtained in the same manner as in Synthesis Example 68 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 679.288
Compound Cpd 432 (11.8 g, yield 82%) was obtained in the same manner as in Synthesis Example 69 except that 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-10-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used instead of 2-(7,7-dimethyl-7H-fluoreno[2,3-b]benzofuran-9-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. HRMS[M]+: 719.319
Compound Cpd 431 (10.4 g, yield 86%) was obtained in the same manner as in Synthesis Example 70 except that Inv 3 was used instead of Inv 1. HRMS[M]+: 603.256
After high purity sublimation purifying Compound Cpd 417 synthesized in Synthesis Example 67 using a commonly known method, a green organic electroluminescent device was manufactured as follows.
A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was ultrasonic cleaned using distilled water. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents of isopropyl alcohol, acetone, methanol and the like, dried, then transferred to a UV OZONE washer (Power sonic 405, manufactured by Hwashin Tech. Co., Ltd.), and then, after cleaning the substrate for 5 minutes using UV, the substrate was transferred to a vacuum deposition apparatus.
On the transparent ITO electrode prepared as above, m-MTDATA (60 nm)/TCTA (80 nm)/Compound Cpd 417 (40 nm)/CBP+10% Ir(ppy)3 (30 nm)/BCP (10 nm)/Alq3(30 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to manufacture an organic electroluminescent device.
Structures of the m-MTDATA, the TCTA, the Ir(ppy)3, the CBP and the BCP used herein are as follows.
Organic EL devices were manufactured in the same manner as in Example 1 except that compounds described in the following Table 1 were each used instead of Compound Cpd 417 used in Example 1.
A green organic electroluminescent device was manufactured in the same manner as in Example 1 except that Compound Cpd 417 used in Example 1 was not used.
For the green organic electroluminescent devices each manufactured in Examples 1 to 8 and Comparative Example 1, driving voltage, current efficiency and light emission peak at current density of 10 mA/cm2 were measured, and the results are shown in the following Table 1.
As shown in Table 1, it was seen that the green organic electroluminescent devices of Examples 1 to 8 using the compound according to the present invention as a light emitting auxiliary layer material had a slightly lower driving voltage compared to the green organic electroluminescent device of Comparative Example 1 using just CBP as a light emitting layer material without a light emitting auxiliary layer, and more superior current efficiency was obtained compared to the green organic electroluminescent device of Comparative Example 1.
After high purity sublimation purifying Compound Cpd 417 synthesized in Synthesis Example 67 using a commonly known method, a red organic electroluminescent device was manufactured as follows.
First, a glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was ultrasonic cleaned using distilled water. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents of isopropyl alcohol, acetone, methanol and the like, dried, then transferred to a UV OZONE washer (Power sonic 405, manufactured by Hwashin Tech. Co., Ltd.), and then, after cleaning the substrate for 5 minutes using UV, the substrate was transferred to a vacuum deposition apparatus.
On the transparent ITO electrode prepared as above, m-MTDATA (60 nm)/TCTA (80 nm)/Compound Cpd 417 (40 nm)/CBP+10% (piq)2Ir(acac) (30 nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to manufacture an organic electroluminescent device.
Structures of the m-MTDATA, the TCTA, the CBP and the BCP used herein are the same as described in Example 1, and a structure of the (piq)2Ir(acac) is as follows.
Red organic EL devices were manufactured in the same manner as in Example 9 except that compounds described in the following Table 2 were each used instead of Compound Cpd 417 used in Example 9.
A red organic electroluminescent device was manufactured in the same manner as in Example 9 except that Compound Cpd 417 used in Example 9 was not used.
For each of the red organic electroluminescent devices manufactured in Examples 9 to 16 and Comparative Example 2, driving voltage and current efficiency at current density of 10 mA/cm2 were measured, and the results are shown in the following Table 2.
As shown in Table 2, it was seen that the red organic electroluminescent devices of Examples 9 to 16 using the compound according to the present invention as alight emitting auxiliary layer material had more superior current efficiency as well as a slightly lower driving voltage compared to the red organic electroluminescent device of Comparative Example 2 using just CBP as a light emitting layer material without a light emitting auxiliary layer.
After high purity sublimation purifying Compound Cpd 10 synthesized in Synthesis Example 1 using a commonly known method, a green organic electroluminescent device was manufactured using the following procedure.
First, a glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was ultrasonic cleaned using distilled water. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents of isopropyl alcohol, acetone, methanol and the like, dried, then transferred to a UV OZONE washer (Power sonic 405, manufactured by Hwashin Tech. Co., Ltd.), and then, after cleaning the substrate for 5 minutes using UV, the substrate was transferred to a vacuum deposition apparatus.
On the transparent ITO electrode prepared as above, m-MTDATA (60 nm)/TCTA (80 nm)/Compound Cpd 10+10% Ir(ppy)3 (30nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to manufacture an organic electroluminescent device.
Green organic EL devices were manufactured in the same manner as in Example 17 except that compounds described in the following Table 3 were each used instead of Compound Cpd 10 used in Example 17.
A green organic EL device was manufactured in the same manner as in Example 17 except that CBP was used instead of Compound Cpd 10 used as a light emitting host material when forming the light emitting layer in Example 17.
For each of the green organic EL devices manufactured in Examples 17 to 75 and Comparative Example 3, driving voltage, current efficiency and light emission peak at current density of 10 mA/cm2 were measured, and the results are shown in the following Table 3.
As shown in Table 3, it was seen that the green organic electroluminescent devices of Examples 17 to 75 each using the compound according to the present invention as a light emitting layer material had more superior performance in terms of current efficiency and driving voltage compared to the green organic EL device of Comparative Example 3 using existing CBP.
After high purity sublimation purifying Compound Cpd 409 synthesized in Synthesis Example 61 using a commonly known method, a red organic electroluminescent device was manufactured using the following procedure.
First, a glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was ultrasonic cleaned using distilled water. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents of isopropyl alcohol, acetone, methanol and the like, dried, then transferred to a UV OZONE washer (Power sonic 405, manufactured by Hwashin Tech. Co., Ltd.), and then, after cleaning the substrate for 5 minutes using UV, the substrate was transferred to a vacuum deposition apparatus.
On the transparent ITO electrode prepared as above, m-MTDATA (60 nm)/TCTA (80 nm)/Compound Cpd 409+10% (piq)2Ir(acac) (30 nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to manufacture an organic electroluminescent device.
A red organic electroluminescent device was manufactured in the same manner as in Example 76 except that CBP was used instead of Compound Cpd 409 used as a light emitting host material when forming the light emitting layer.
Red organic EL devices were manufactured in the same manner as in Example 76 except that compounds described in the following Table 4 were each used instead of Compound Cpd 409 used in Example 76.
For each of the organic electroluminescent devices manufactured in Examples 76 to 81 and Comparative Example 4, driving voltage and current efficiency at current density of 10 mA/cm2 were measured, and the results are shown in the following Table 4.
As shown in Table 4, it was seen that, when using the compound according to the present invention as a light emitting layer material of the red organic electroluminescent device (Examples 76 to 81), more superior performance was obtained in terms of efficiency and driving voltage compared to the red organic electroluminescent device (Comparative Example 4) using existing CBP as a light emitting layer material.
After high purity sublimation purifying Compound Cpd 10 synthesized in Synthesis Example 1 using a commonly known method, a blue organic electroluminescent device was manufactured as follows.
A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was ultrasonic cleaned using distilled water. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents of isopropyl alcohol, acetone, methanol and the like, dried, then transferred to a UV OZONE washer (Power sonic 405, manufactured by Hwashin Tech. Co., Ltd.), and then, after cleaning the substrate for 5 minutes using UV, the substrate was transferred to a vacuum deposition apparatus.
On the transparent ITO electrode prepared as above, DS-205 (80 nm)/NPB (15 nm)/AND+5% DS-405 (30 nm)/Compound Cpd10 (5 nm)/Alq3 (25 nm)/LiF (1 nm)/Al (200 nm) were laminated in this order to manufacture an organic electroluminescent device.
Blue organic EL devices were manufactured in the same manner as in Example 82 except that each compound described in the following Table 5 was used instead of Compound Cpd 10 used as a hole blocking layer material in Example 82.
A blue organic electroluminescent device was manufactured in the same manner as in Example 82 except that Compound Cpd 10 used as a hole blocking layer material in Example 82 was not used, and Alq3, the electron transport layer material, was deposited to 30 nm instead of 25 nm.
An organic electroluminescent device was manufactured in the same manner as in Example 83 except that BCP was used instead of not using Compound Cpd 10 used as a hole blocking layer material.
For the organic electroluminescent devices each manufactured in Examples 82 to 137 and Comparative Examples 5 and 6, driving voltage, current efficiency, light emission peak and lifetime (T97) at current density of 10 mA/cm2 were measured, and the results are shown in the following Table 5.
As shown in Table 5, it was seen that the blue organic EL devices of Examples 82 to 137 using the compound according to the present invention as a hole blocking layer material had a similar or slightly superior driving voltage compared to the blue organic EL device of Comparative Example 5 not using the hole blocking layer, but had significantly enhanced current efficiency and lifetime.
In addition, compared to the blue organic EL device of Comparative Example 6 using existing CBP as a hole blocking layer material instead of the hole blocking layer, a significantly enhanced lifetime was obtained as well as excellent driving voltage and current efficiency.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0089032 | Jul 2017 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/007734 | 7/9/2018 | WO | 00 |
