# Patent

## Title
Compound wherein substituted bipyridyl group is connected with pyridoindole ring structure through phenylene group, and organic electroluminescent device

## Abstract

An organic compound is provided having excellent electron-injection/transport performance, hole-blocking ability, and high stability in a thin-film state. An organic electroluminescence device having a high efficiency and a high durability is provided, using the compound. The compound has a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, is of formula (1). The organic EL device has a pair of electrodes and at least one organic layer interposed between the electrodes, wherein the compound is a constituent material for an organic layer therein.

## Background
TECHNICAL FIELD
The present invention relates to a compound suitable for an organic electroluminescence (EL) device which is a self-luminescent device suitable for various displaying devices and a device. More specifically, it relates to a compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group and to an organic EL device using the compound.
BACKGROUND ART
Since organic EL devices are self-luminescent devices, they are bright and excellent in visibility as compared with liquid-crystalline devices and capable of giving clear display, so that the organic EL devices have been actively studied.
In 1987, C. W. Tang et al. of Eastman Kodak Company put an organic EL device using organic materials into practical use by developing a device having a multilayered structure wherein various roles are assigned to respective materials. They formed a lamination of a fluorescent material capable of transporting electrons and an organic material capable of transporting holes, so that both charges are injected into the layer of the fluorescent material to emit light, thereby achieving a high luminance of 1000 cd/m2 or more at a voltage of 10 V or lower (see e.g., Patent Documents 1 and 2).

    Patent Document 1: JP-A-8-48656
    Patent Document 2: Japanese Patent No. 3194657


To date, many improvements have been performed for practical utilization of the organic EL devices, and high efficiency and durability have been achieved by an electroluminescent device wherein an anode, a hole-injecting layer, a hole-transporting layer, an emitting layer, an electron-transporting layer, an electron-injecting layer, and a cathode are sequentially provided on a substrate, to further segmentalize various roles (see e.g., Non-Patent Document 1).

    Non-Patent Document 1: Japan Society of Applied Physics Ninth Workshop Preprint, pp. 55-61 (2001)


Moreover, for the purpose of further improvement of luminous efficiency, utilization of triplet exciton has been attempted and utilization of a phosphorescent material has been investigated (see e.g., Non-Patent Document 2).

    Non-Patent Document 2: Japan Society of Applied Physics Ninth Workshop Preprint, pp. 23-31 (2001)


The emitting layer can be also prepared by doping a charge-transporting compound, generally called a host material, with a fluorescent material or a phosphorescent material. As described in the above-mentioned Workshop Preprints, the choice of the organic materials in organic EL devices remarkably affects various properties such as efficiency and durability of the devices.
In the organic EL devices, the charges injected from the both electrode are recombined in the emitting layer to attain light emission. However, since the mobility of holes is higher than the mobility of electrons, a problem of reduction in efficiency caused by a part of the holes passing through the emitting layer arises. Therefore, it is required to develop an electron-transporting material in which the mobility of electrons is high.
A representative light-emitting material, tris(8-hydroxyquinoline)aluminum (hereinafter referred to as Alq3) is commonly used also as an electron-transporting material but it cannot be considered that the material has hole-blocking capability.
As a technique to prevent the passing of a part of holes through the emitting layer and to improve probability of charge recombination in the emitting layer, there is a method of inserting a hole-blocking layer. As hole-blocking materials, there have been hitherto proposed triazole derivatives (see e.g., Patent Document 3), bathocuproine (hereinafter referred to as BCP), a mixed ligand complex of aluminum (BAlq) (see e.g., Non-Patent Document 2), and the like.
For example, as an electron-transporting material excellent in hole-blocking ability, there is proposed 3-(4-biphenyl)-1)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (hereinafter referred to as TAZ) (see e.g., Patent Document 3).

    Patent Document 3: Japanese Patent No. 2734341


Since TAZ has a work function as large as 6.6 eV and thus exhibits a high hole-blocking ability, it is used as an electron-transporting hole-blocking layer to be laminated onto the cathode side of a fluorescence-emitting layer or phosphorescence-emitting layer prepared by vacuum deposition, coating or the like, and contributes to increase the efficiency of organic EL devices (see e.g., Non-Patent Document 3).

    Non-Patent Document 3: Fiftieth Meeting of Japan Society of Applied Physics and Related Societies, 28p-A-6 Lecture Preprint, p. 1413 (2003)


However, TAZ has a great problem of having low electron transport property, and it is necessary to prepare an organic EL device in combination with an electron-transporting material having a higher electron transport property (see e.g., Non-Patent Document 4).

    Non-Patent Document 4: Japan Society of Applied Physics, Journal of Organic Molecules/Bioelectronics Section, Vol. 11, No. 1, pp. 13-19 (2000)


Further, BCP has a work function as large as 6.7 eV and a high hole-blocking ability, but has a low glass transition point (Tg) which is 83° C., so that it is poor in thin-film stability and thus it cannot be considered that it sufficiently functions as a hole-blocking layer.
All the materials are insufficient in film stability or are insufficient in the function of blocking holes. In order to improve characteristic properties of the organic EL devices, it is desired to develop an organic compound which is excellent in electron-injection/transport performances and hole-blocking ability and is highly stable in a thin-film state.
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
Objects of the present invention are to provide an organic compound having excellent properties, which is excellent in electron-injection/transport performances, has hole-blocking ability and is highly stable in a thin-film state, as a material for an organic electroluminescence device having a high efficiency and a high durability, and to provide an organic electroluminescence device having a high efficiency and a high durability using the compound.
As physical properties of the organic compound to be provided by the invention, there may be mentioned (1) good electron injection characteristic, (2) high electron mobility, (3) excellent hole-blocking ability, (4) good stability in a thin-film state, and (5) excellent thermal resistance. In addition, as physical properties of the organic EL device to be provided by the invention, there may be mentioned (1) high luminous efficiency, (2) low emission initiation voltage, (3) low practical driving voltage, and (4) high maximum emission luminance.
Means for Solving the Problems
Thus, in order to achieve the above objects, the present inventors have designed and chemically synthesized compounds having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, with focusing on the fact that the nitrogen atom of the pyridine ring which exhibits affinity to an electron has an ability of coordinating to a metal and is excellent in thermal resistance. The present inventors have experimentally produced various organic EL devices using the compounds, and have extensively performed property evaluation of the devices. As a result, they have accomplished the invention.
Namely, the invention provides a compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1). Also, the invention provides an organic EL device comprising a pair of electrodes and at least one organic layer interposed between the electrodes, wherein the compound is used as a constituent material for the at least one organic layer:




wherein Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group; R1 to R17 may be the same or different and represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group; and W, X, Y, and Z represent a carbon atom or a nitrogen atom; provided that only one of W, X, Y, and Z is a nitrogen atom and the nitrogen atom does not have a substituent of R10, R11, R12, or R13.

The “aromatic hydrocarbon group”, “aromatic heterocyclic group” and “condensed polycyclic aromatic group” in the substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted aromatic heterocyclic group, or substituted or unsubstituted condensed polycyclic aromatic group, which is represented by Ar in the general formula (1) specifically includes a phenyl group, a biphenyl group, a terphenyl group, a tetrakisphenyl group, a styryl group, a naphthyl group, an anthryl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a pyridyl group, a pyrimidyl group, a pyridoindolyl group, a furanyl group, a pyranyl group, a thiophenyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthyridinyl group, a phenanthrolinyl group, and an acridinyl group.
The “substituent” in the substituted aromatic hydrocarbon group, substituted aromatic heterocyclic group, and substituted condensed polycyclic aromatic group represented by Ar in the general formula (1) specifically includes groups such as a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an amino group, a phenyl group, a naphthyl group, an anthryl group, a styryl group, a pyridyl group, a pyridoindolyl group, a quinolyl group, and a benzothiazolyl group. These substituents may be further substituted.
The “aromatic hydrocarbon group” in the substituted or unsubstituted aromatic hydrocarbon group represented by R1 to R17 in the general formula (1) specifically includes a phenyl group, a biphenyl group, a terphenyl group, a tetrakisphenyl group, a styryl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an indenyl group, and a pyrenyl group.
The “substituent” in the substituted aromatic hydrocarbon group represented by R1 to R17 in the general formula (1) specifically includes a fluorine atom, a chlorine atom, a trifluoromethyl group, and a linear or branched alkyl group having 1 to 6 carbon atoms. These substituents may be further substituted.
The compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1) of the invention, provides high electron mobility as compared with conventional electron-transporting materials, has an excellent hole-blocking ability, and is stable in a thin-film state.
The compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1) of the invention, can be used as a constituent material for an electron-transporting layer of an organic EL device. The use of the material exhibiting a higher electron injection/mobile rate as compared with conventional materials provides effects of improving electron transport efficiency from the electron-transporting layer to an emitting layer to enhance luminous efficiency and also lowering a driving voltage to enhance durability of the organic EL device.
The compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1) of the invention, can be also used as a constituent material for a hole-blocking layer of an organic EL device. The use of the material excellent in hole-blocking ability and also excellent in electron transport property as compared with conventional materials and having high stability in a thin-film state provides effects of lowering a driving voltage, improving current resistance, and enhancing maximum emission luminance of the organic EL device, while exhibiting high luminous efficiency.
The compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1) of the invention, can be also used as a constituent material for an emitting layer of an organic EL device. The use of an emitting layer prepared by using the material of the invention excellent in electron transport property as compared with conventional materials and having a wide band-gap as a host material for the emitting layer and making a fluorescent material or a phosphorescent material, called a dopant, carried thereon provides an effect of realizing an organic EL device exhibiting a lowered driving voltage and having improved luminous efficiency.
Advantageous Effects of the Invention
According to the invention, there is provided a compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is useful as a constituent material for an electron-transporting layer, a hole-blocking layer, or an emitting layer of an organic EL device. Further, since the organic EL device prepared by using the compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group exhibits high electron mobility as compared with conventional electron-transporting materials, has an excellent hole-blocking ability, and is stable in a thin-film state, it becomes possible to realize a high efficiency and a high durability.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a 1H-NMR chart of the compound (Compound 36) of Invention Example 1.
FIG. 2 is a 1H-NMR chart of the compound (Compound 40) of Invention Example 2.
FIG. 3 is a 1H-NMR chart of the compound (Compound 164) of Invention Example 3.
FIG. 4 is a 1H-NMR chart of the compound (Compound 20) of Invention Example 4.
FIG. 5 is a 1H-NMR chart of the compound (Compound 24) of Invention Example 5.
FIG. 6 is a 1H-NMR chart of the compound (Compound 37) of Invention Example 6.
FIG. 7 is a 1H-NMR chart of the compound (Compound 41) of Invention Example 7.
FIG. 8 is a 1H-NMR chart of the compound (Compound 52) of Invention Example 8.
FIG. 9 is a 1H-NMR chart of the compound (Compound 72) of Invention Example 9.
FIG. 10 is a 1H-NMR chart of the compound (Compound 116) of Invention Example 10.
FIG. 11 is a 1H-NMR chart of the compound (Compound 165) of Invention Example 11.
FIG. 12 is a 1H-NMR chart of the compound (Compound 192) of Invention Example 12.
FIG. 13 is a 1H-NMR chart of the compound (Compound 193) of Invention Example 13.
FIG. 14 is a drawing showing the constitution of the EL devices of Examples 16 to 24.
FIG. 15 is a drawing showing the constitution of the EL device of Comparative Example 1.



DESCRIPTION OF REFERENCE NUMERALS AND SIGNS


    
    
        1: Glass substrate
        2: Transparent anode
        3: Hole-injecting layer
        4: Hole-transporting layer
        5: Emitting layer
        6: Hole-blocking layer
        7: Electron-transporting layer
        8: Electron-injecting layer
        9: Cathode
    
    


BEST MODE FOR CARRYING OUT THE INVENTION
The compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group according to the invention is a novel compound, and the compound can be synthesized, for example, by subjecting a corresponding halogenoanilinopyridine to a cyclization reaction with a palladium catalyst to synthesize a pyridoindol ring (see e.g., Non-Patent Document 5) and then by condensing it with one of various halogenophenylenes having a substituted bipyridyl group to synthesize a compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group. Each of the various halogenophenylenes having a bipyridyl group can be synthesized by condensing a corresponding aldehyde and an acetylpyridine in the presence of a base and further reacting the resulting product with a corresponding pyridinium iodide (see e.g., Non-Patent Document 6).

    Non-Patent Document 5: J. Chem. Soc., Perkin Trans. 1, p. 1505 (1999)
    Non-Patent Document 6: Synthesis, 1 (1976)


Among the compounds having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, which is represented by the general formula (1), specific examples of preferred compounds are shown below, but the invention is not limited to these compounds.

































































































































































































Purification of these compounds was performed by purification by column chromatography, adsorption purification, a recrystallization or crystallization method with a solvent, or the like. Identification of the compounds can be performed by NMR analysis. As physical properties, DSC measurement (Tg) and measurement of melting point were performed. The melting point serves as an index of vapor deposition properties and the glass transition point (Tg) serves as an index of stability in a thin-film state.
The melting point and the glass transition point were measured using a powder material by means of a highly sensitive differential scanning calorimeter DSC 31005 manufactured by Bruker AXS.
Further, the work function was measured by preparing a thin film of 100 nm on an ITO substrate and using a photo-electron spectroscopy in air (Model AC-3, manufactured by Riken Keiki Co., Ltd.). The work function is regarded as an indicator of hole-blocking ability.
Examples of the structure of the organic EL device of the invention include a structure having an anode, a hole-injecting layer, a hole-transporting layer, an emitting layer, a hole-blocking layer, an electron-transporting layer and a cathode in this order on a substrate, and a structure further having an electron-injecting layer between the electron-transporting layer and the cathode. In these multilayer structures, it is possible to omit several layers of the organic layers and, for example, the structure may have a constitution sequentially having an anode, a hole-transporting layer, an emitting layer, an electron-transporting layer and a cathode on a substrate.
As the anode of the organic EL device, an electrode material having a large work function, such as ITO or gold, is used. As the hole-injecting layer, besides copper phthalocyanine (hereinafter referred to as CuPc), materials such as star-burst type triphenylamine derivatives and wet-process type materials may be employed.
For the hole-transporting layer, N,N′-diphenyl-N,N′-di(m-tolyl)-benzidine (hereinafter referred to as TPD) and N,N′-diphenyl-N,N′-di(α-naphthyl)-benzidine (hereinafter referred to as NPD), various triphenylamine tetramers, and the like may be used. Further, as the hole-injecting/transporting layers, wet-process type polymer materials such as PEDOT/PSS may be employed.
As the emitting layer, hole-blocking layer, and electron-transporting layer of the organic EL device of the invention, besides the compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group, aluminum complexes, thiazole derivatives, oxazole derivatives, carbazole derivatives, polydialkylfluorene derivatives, and the like may be used.
By using a conventional luminescence material such as an aluminum complex or styryl derivative for the emitting layer and using the compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group as the hole-blocking layer and the electron-transporting layer, a high-performance organic EL device can be prepared. Further, a high-performance organic EL device can be prepared also by adding a dopant, for example, a fluorescent material such as quinacridone, coumarin or rubrene or a phosphorescent material such as an iridium complex of phenylpyridine, as a host material of the emitting layer.
Furthermore, the compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group can be used as the electron-transporting layer through multilayering or co-deposition with conventional electron-transporting material(s).
The organic EL device of the invention may have an electron-injecting layer. As the electron-injecting layer, lithium fluoride or the like may be used. For the cathode, an electrode material having a low work function such as aluminum, or an alloy having a low work function such as aluminum magnesium is used as an electrode material.
Embodiments of the invention will be illustrated in greater detail with reference to Examples, but the invention should not be construed as being limited to the following Examples so long as not exceeding the gist thereof.
Example 1
Synthesis of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 36)
10.0 g of 4′-bromoacetophenone, 12.8 g of iodine, and 80 ml of pyridine were added and the whole was heated and stirred at 100° C. for 3 hours. After cooling to room temperature, 100 ml of water was added and purification by recrystallization was performed. Drying was performed under reduced pressure at 70° C. for 12 hours to obtain 15.5 g (yield 76%) of 4-bromophenacylpyridinium iodide as a brown powder.
Subsequently, 6.0 g of 2-naphthoaldehyde, 4.7 g of 2-acetylpyridine, and 40 ml of methanol were added and the whole was cooled to −5° C. under stirring. 62 ml of a 3 wt % NaOH/methanol solution was added dropwise thereto and the whole was stirred at −5° C. for 2 hours. Then, the reaction was further carried out at the same temperature for 2 days. 37.0 g of ammonium acetate, 15.5 g of the above 4-bromophenacylpyridinium iodide, and 100 ml of methanol were added to the reaction solution and the whole was stirred at 55° C. for 2 days. After cooling to room temperature, the resulting crude product was collected by filtration, washed with methanol, and then dried under reduced pressure at 70° C. for 12 hours to obtain 3.8 g (yield 23%) of 6-(4-bromophenyl)-4-(naphthalen-2-yl)-[2,2′]bipyridine as a gray powder.
2.5 g of the resulting 6-(4-bromophenyl)-4-(naphthalen-2-yl)-[2,2′]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.4 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 7 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 1.85 g (yield 62%) of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 36) as a white powder.
The structure of the resulting white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 1.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.42 (1H), 8.85 (1H), 8.76 (2H), 8.49-8.57 (3H), 8.36 (1H), 8.20-8.25 (2H), 7.90-8.03 (5H), 7.73 (2H), 7.51-7.58 (4H), 7.38-7.42 (3H).
Example 2
Synthesis of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 40)
4-(4-Bromophenyl)-6-(naphthalen-2-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.5 g of the resulting 4-(4-bromophenyl)-6-(naphthalen-2-yl)-[2,2′]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.4 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 9 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 2.17 g (yield 72%) of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 40) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 2.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.42 (1H), 8.76-8.80 (3H), 8.70 (1H), 8.57 (1H), 8.42 (1H), 8.22-8.25 (2H), 8.12 (2H), 8.03 (2H), 7.92-7.94 (2H), 7.73 (2H), 7.53-7.57 (4H), 7.38-7.43 (3H).
Example 3
Synthesis of 4,6-bis[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 164)
4,6-Bis(4-bromophenyl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 1.8 g of the resulting 4,6-bis(4-bromophenyl)-[2,2′]bipyridine, 1.4 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 1.6 g of potassium carbonate, 0.1 ml of dimethyl sulfoxide, and 5 ml of n-dodecane were added and the whole was stirred for 11 hours under heating and refluxing. After cooling to room temperature, 50 ml of methanol was added thereto and insoluble solid was removed by filtration. 300 ml of chloroform was added to the insoluble solid and extraction was performed. The extraction liquid was concentrated under reduced pressure to obtain a crude product. The crude product was subjected to purification using o-dichlorobenzene as a recrystallization solvent and drying was performed under reduced pressure at 70° C. for 12 hours to obtain 1.45 g (yield 58%) of 4,6-bis[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 164) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 3.
The following 28 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.43 (2H), 8.76-8.84 (3H), 8.52-8.59 (4H), 8.14-8.26 (5H), 7.94 (1H), 7.76 (4H), 7.52-7.57 (4H), 7.39-7.44 (5H).
Example 4
Synthesis of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(naphthalen-1-yl)-[2,2′]bipyridine (Compound 20)
6-(4-Bromophenyl)-4-(naphthalen-1-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.2 g of the resulting 6-(4-bromophenyl)-4-(naphthalen-1-yl)-[2,2′]bipyridine, 0.9 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.1 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 6 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 2.02 g (yield 77%) of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(naphthalen-1-yl)-[2,2′]bipyridine (Compound 20) as a brown-white powder.
The structure of the resulting brown-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 4.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.41 (1H), 8.77 (1H), 8.70 (1H), 8.64 (1H), 8.56 (1H), 8.48 (2H), 8.24 (1H), 8.03 (1H), 7.90-8.00 (4H), 7.71 (2H), 7.50-7.61 (6H), 7.36-7.42 (3H).
Example 5
Synthesis of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(naphthalen-1-yl)-[2,2]bipyridine (Compound 24)
4-(4-Bromophenyl)-6-(naphthalen-1-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.2 g of the resulting 4-(4-bromophenyl)-6-(naphthalen-1-yl)-[2,2′]bipyridine, 0.9 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.1 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 5 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 2.04 g (yield 77%) of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(naphthalen-1-yl)-[2,2′]bipyridine (Compound 24) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 5.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.41 (1H), 8.86 (1H), 8.76 (1H), 8.60 (1H), 8.56 (1H), 8.35 (1H), 8.23 (1H), 8.10 (2H), 7.99 (2H), 7.94 (1H), 7.80-7.85 (2H), 7.71 (2H), 7.64 (1H), 7.52-7.57 (4H), 7.36-7.43 (3H).
Example 6
Synthesis of 6-[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-4-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 37)
6-(4-Bromophenyl)-4-(naphthalen-2-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.5 g of the resulting 6-(4-bromophenyl)-4-(naphthalen-2-yl)-[2,2′]bipyridine, 1.0 g of 5H-pyrido[3,2-b]indole, 0.2 g of copper powder, 2.4 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 19 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was subjected to purification using o-dichlorobenzene as a recrystallization solvent and drying was performed under reduced pressure at 70° C. for 12 hours to obtain 1.03 g (yield 34%) of 6-[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-4-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 37) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 6.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=8.85 (1H), 8.78 (1H), 8.75 (1H), 8.65 (1H), 8.48-8.50 (3H), 8.36 (1H), 8.21 (1H), 7.98-8.03 (3H), 7.90-7.94 (2H), 7.81 (1H), 7.74 (2H), 7.55-7.60 (4H), 7.36-7.43 (3H).
Example 7
Synthesis of 4-[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-6-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 41)
4-(4-Bromophenyl)-6-(naphthalen-2-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.5 g of the resulting 4-(4-bromophenyl)-6-(naphthalen-2-yl)-[2,2]bipyridine, 1.1 g of 5H-pyrido[3,2-b]indole, 0.2 g of copper powder, 2.4 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 18 hours under heating and refluxing. After cooling to room temperature, 60 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 1.86 g (yield 62%) of 4-[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-6-(naphthalen-2-yl)-[2,2′]bipyridine (Compound 41) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 7.
The following 24 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=8.76-8.80 (3H), 8.70 (1H), 8.65 (1H), 8.48 (1H), 8.42 (1H), 8.21 (1H), 8.10 (1H), 8.02 (2H), 7.92 (2H), 7.79 (1H), 7.73 (2H), 7.55-7.57 (4H), 7.36-7.44 (3H).
Example 8
Synthesis of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(phenanthren-9-yl)-[2,2′]bipyridine (Compound 52)
6-(4-Bromophenyl)-4-(phenanthren-9-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.6 g of the resulting 6-(4-bromophenyl)-4-(phenanthren-9-yl)-[2,2]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.2 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 5 hours under heating and refluxing. After cooling to room temperature, 80 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene) to obtain 2.35 g (yield 78%) of 6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-4-(phenanthren-9-yl)-[2,2′]bipyridine (Compound 52) as a pale red-white powder.
The structure of the resulting pale red-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 8.
The following 26 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.41 (1H), 8.83 (1H), 8.78 (2H), 8.70-8.72 (2H), 8.55 (1H), 8.49 (2H), 8.23 (1H), 8.08 (1H), 8.01 (1H), 7.91-7.96 (2H), 7.88 (1H), 7.71-7.75 (4H), 7.67 (1H), 7.61 (1H), 7.50-7.55 (2H), 7.37-7.41 (3H).
Example 9
Synthesis of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(phenanthren-2-yl)-[2,2]bipyridine (Compound 72)
4-(4-Bromophenyl)-6-(phenanthren-2-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.6 g of the resulting 4-(4-bromophenyl)-6-(phenanthren-2-yl)-[2,2]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.2 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 6 hours under heating and refluxing. After cooling to room temperature, 80 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 1.40 g (yield 47%) of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(phenanthren-2-yl)-[2,2′]bipyridine (Compound 72) as a pale red-white powder.
The structure of the resulting pale red-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 9.
The following 26 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.42 (1H), 8.75-8.86 (6H), 8.57 (2H), 8.24 (2H), 8.12 (2H), 7.91-7.95 (3H), 7.82 (1H), 7.63-7.73 (4H), 7.54 (2H), 7.38-7.43 (3H).
Example 10
Synthesis of 4-(biphenyl-4-yl)-6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2]bipyridine (Compound 116)
4-(Biphenyl-4-yl)-6-(4-bromophenyl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.5 g of the resulting 4-(biphenyl-4-yl)-6-(4-bromophenyl)-[2,2′]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.3 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 5 hours under heating and refluxing. After cooling to room temperature, 80 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene/ethyl acetate) to obtain 2.81 g (yield 93%) of 4-(biphenyl-4-yl)-6-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 116) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 10.
The following 26 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.41 (1H), 8.78 (1H), 8.76 (1H), 8.73 (1H), 8.56 (1H), 8.49 (2H), 8.24 (1H), 8.13 (1H), 7.96 (2H), 7.91 (1H), 7.79 (2H), 7.73 (2H), 7.69 (2H), 7.48-7.56 (4H), 7.37-7.42 (4H).
Example 11
Synthesis of 4,6-bis[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 165)
4,6-Bis(4-bromophenyl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.2 g of the resulting 4,6-bis(4-bromophenyl)-[2,2′]bipyridine, 1.7 g of 5H-pyrido[3,2-b]indole, 0.2 g of copper powder, 2.0 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 18 hours under heating and refluxing. After cooling to room temperature, 50 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 1.50 g (yield 50%) of 4,6-bis[4-(5H-pyrido[3,2-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 165) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 11.
The following 28 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=8.83 (1H), 8.76-8.78 (2H), 8.66 (2H), 8.48-8.52 (4H), 8.17 (1H), 8.13 (2H), 7.94 (1H), 7.81 (2H), 7.76 (4H), 7.56-7.61 (4H), 7.36-7.44 (5H).
Example 12
Synthesis of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(phenanthren-9-yl)-[2,2]bipyridine (Compound 192)
4-(4-Bromophenyl)-6-(phenanthren-9-yl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.2 g of the resulting 4-(4-bromophenyl)-6-(phenanthren-9-yl)-[2,2′]bipyridine, 0.8 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 1.8 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 8 hours under heating and refluxing. After cooling to room temperature, 80 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: hexane/chloroform) to obtain 1.36 g (yield 54%) of 4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-6-(phenanthren-9-yl)-[2,2′]bipyridine (Compound 192) as a yellow-white powder.
The structure of the resulting yellow-white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 12.
The following 26 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.40 (1H), 8.89 (1H), 8.84 (1H), 8.78 (2H), 8.61 (1H), 8.55 (1H), 8.32 (1H), 8.23 (1H), 8.12 (2H), 8.04 (1H), 7.99 (2H), 7.83 (1H), 7.71-7.74 (4H), 7.62-7.67 (2H), 7.52 (2H), 7.37-7.42 (3H).
Example 13
Synthesis of 6-(biphenyl-4-yl)-4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2]bipyridine (Compound 193)
6-(Biphenyl-4-yl)-4-(4-bromophenyl)-[2,2′]bipyridine was synthesized in the same manner as in the above Example 1. 2.5 g of the resulting 6-(biphenyl-4-yl)-4-(4-bromophenyl)-[2,2′]bipyridine, 1.0 g of 5H-pyrido[4,3-b]indole, 0.2 g of copper powder, 2.3 g of potassium carbonate, 0.2 ml of dimethyl sulfoxide, and 10 ml of n-dodecane were added and the whole was stirred for 7 hours under heating and refluxing. After cooling to room temperature, 80 ml of chloroform was added thereto, insoluble solid was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (carrier: NH silica gel, eluent: toluene/ethyl acetate) to obtain 1.96 g (yield 65%) of 6-(biphenyl-4-yl)-4-[4-(5H-pyrido[4,3-b]indol-5-yl)phenyl]-[2,2′]bipyridine (Compound 193) as a white powder.
The structure of the resulting white powder was identified using NMR. The results of 1H-NMR measurement are shown in FIG. 13.
The following 26 hydrogen signals were detected on 1H-NMR (CDCl3). δ (ppm)=9.42 (1H), 8.76 (3H), 8.57 (1H), 8.34 (2H), 8.25 (1H), 8.11 (3H), 7.91 (1H), 7.80 (2H), 7.70-7.73 (4H), 7.49-7.53 (4H), 7.38-7.43 (4H).
Example 14
For the compounds of the invention, melting point and glass transition point were determined by means of a highly sensitive differential scanning calorimeter (DSC 3100S manufactured by Bruker AXS). The results are shown in Table 1.










TABLE 1








Glass



Melting
Transition



Point
Point




















Compound of Example 1
244° C.
114° C.



Compound of Example 2
253° C.
117° C.



Compound of Example 3
339° C.
161° C.



Compound of Example 4
152° C.
115° C.



Compound of Example 5
151° C.
116° C.



Compound of Example 6
218° C.
108° C.



Compound of Example 7
248° C.
110° C.



Compound of Example 8
181° C.
139° C.



Compound of Example 9
271° C.
139° C.



Compound of Example 10
150° C.
112° C.



Compound of Example 11
343° C.
155° C.



Compound of Example 12
186° C.
132° C.



Compound of Example 13
231° C.
114° C.










The compounds of the invention show a glass transition point of 100° C. or higher, and thus are stable in a thin-film state.
Example 15
Using each of the compounds of the invention, a deposited film having a film thickness of 100 nm was prepared on an ITO substrate and work function was measured on a photo-electron spectroscopy in air (Model AC-3, manufactured by Riken Keiki Co., Ltd.). The results are shown in Table 2.









TABLE 2







Work



Function



















Compound of Example 1
6.11 eV



Compound of Example 2
6.18 eV



Compound of Example 3
6.15 eV



Compound of Example 4
6.25 eV



Compound of Example 5
6.33 eV



Compound of Example 6
5.99 eV



Compound of Example 7
6.12 eV



Compound of Example 8
6.27 eV



Compound of Example 9
6.34 eV



Compound of Example 10
6.27 eV



Compound of Example 11
6.15 eV



Compound of Example 12
6.37 eV



Compound of Example 13
6.16 eV










Thus, the compounds of the invention have values deeper than a work function of 5.4 eV possessed by common hole-transporting materials such as NPD and TPD and have a large hole-blocking ability.
Example 16
An organic EL device was prepared by depositing a hole-injecting layer 3, a hole-transporting layer 4, an emitting layer 5, a hole-blocking layer 6, an electron-transporting layer 7, an electron-injecting layer 8, and a cathode (aluminum electrode) 9 in this order on a glass substrate 1 on which an ITO electrode had been formed as a transparent anode 2 in advance, as shown in FIG. 14.
After the glass substrate 1 on which ITO having a film thickness of 150 nm had been formed was washed with an organic solvent, the surface was washed by UV ozone treatment. It was mounted in a vacuum deposition machine, which was then evacuated to 0.001 Pa or lower.
Subsequently, copper phthalocyanine was formed thereon at a deposition rate of 3.6 nm/min to a thickness of about 20 nm as the hole-injecting layer 3. NPD was formed on the hole-injecting layer 3 at a deposition rate of 3.6 nm/min to a thickness of about 40 nm as the hole-transporting layer 4. As the emitting layer 5, Alq3 was formed on the hole-transporting layer 4 at a deposition rate of 3.6 nm/min to a thickness of about 30 nm. On the emitting layer 5, the compound of invention Example 1 (Compound 36) was formed at a deposition rate of 3.6 nm/min to a thickness of about 30 nm as the hole-blocking layer-cum-electron-transporting layer 6 and 7. On the hole-blocking layer-cum-electron-transporting layer 6 and 7, lithium fluoride was formed at a deposition rate of 0.36 nm/min to a thickness of about 0.5 nm as the electron-injecting layer 8. Finally, aluminum was deposited to a thickness of about 200 nm to form the cathode 9. The prepared device was stored in a vacuum desiccator and characteristic properties were measured in the atmosphere at ordinary temperature.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 1 (Compound 36) of the invention are summarized in Table 3.
Example 17
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 2 (Compound 40), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 2 (Compound 40) of the invention are summarized in Table 3.
Example 18
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 10 (Compound 116), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 10 (Compound 116) of the invention are summarized in Table 3.
Comparative Example 1
For comparison, an organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by Alq3 as the electron-transporting layer 7, and characteristic properties thereof were investigated. The results of measurement are shown in Tables 3 and 4.













TABLE 3










Luminous
Power





Luminance
Efficiency
efficiency




Voltage [V]
[cd/m2]
[cd/A]
[lm/W]



Compound
(@10 mA/cm2)
(@10 mA/cm2)
(@10 mA/cm2)
(@10 mA/cm2)





















Example 16
Compound 36
5.90
480
4.80
2.54


Example 17
Compound 40
6.05
460
4.60
2.38


Example 18
Compound
6.35
464
4.64
2.29



116


Comparative
Alq3
6.60
450
4.50
2.13


Example 1









Thus, it was revealed that the organic EL devices of the invention are excellent in luminous efficiency and can achieve remarkable decrease in driving voltage, as compared with the devices using Alq3 which is a commonly employed general electron-transporting material.
Example 19
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 3 (Compound 164), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 3 (Compound 164) of the invention are summarized in Table 4.
Example 20
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 5 (Compound 24), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 5 (Compound 24) of the invention are summarized in Table 4.
Example 21
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 6 (Compound 37), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 6 (Compound 37) of the invention are summarized in Table 4.
Example 22
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 7 (Compound 41), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 7 (Compound 41) of the invention are summarized in Table 4.
Example 23
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 12 (Compound 192), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 12 (Compound 192) of the invention are summarized in Table 4.
Example 24
An organic EL device was prepared under the same conditions as in Example 16 except that the material of the hole-blocking layer-cum-electron-transporting layer 6 and 7 was replaced by the compound of invention Example 13 (Compound 193), and characteristic properties thereof were investigated.
The results of measuring luminescence properties when direct voltage was applied to the organic EL device prepared using the compound of invention Example 13 (Compound 193) of the invention are summarized in Table 4.












TABLE 4









Luminous
Power




Luminance
Efficiency
efficiency




[cd/m2]
[cd/A]
[lm/W]




(@10 mA/
(@10 mA/
(@10 mA/



Compound
cm2)
cm2)
cm2)




















Example 19
Compound 164
515
5.15
2.32


Example 20
Compound 24
495
4.95
2.30


Example 21
Compound 37
485
4.85
1.81


Example 22
Compound 41
465
4.65
1.59


Example 23
Compound 192
490
4.90
2.06


Example 24
Compound 193
455
4.55
2.04


Comparative
Alq3
450
4.50
2.13


Example 1









Thus, it was revealed that the organic EL devices of the invention have high luminance per unit current density and are excellent in luminous efficiency, as compared with the devices using Alq3 which is a commonly employed general electron-transporting material.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
The present application is based on Japanese Patent Application No. 2007-066214 filed on Mar. 15, 2007, and the contents are incorporated herein by reference.
INDUSTRIAL APPLICABILITY
Since the compound having a substituted bipyridyl group and a pyridoindole ring structure connected with each other through a phenylene group according to the invention exhibits a good injection property of electrons and is stable in a thin-film state, the compound is excellent as a compound for organic EL devices. By preparing organic EL devices using the compound, driving voltage can be decreased and durability can be improved. For example, it becomes possible to spread the applications onto electric home appliances and illumination.

## Claims

1. A compound, having:
a substituted bipyridyl group;
a phenylene group; and
a pyridoindole ring structure,
wherein the bipyridyl group and the pyridoindole ring structure are connected with each other through phenylene group, and
wherein the compound is represented by the following formula (1):




wherein
Ar represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, provided that Ar is not pyridyl,
R1 to R17 are the same or different and represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group, and
W, X, Y, and Z represent a carbon atom or a nitrogen atom,
provided that only one of W, X, Y, and Z is a nitrogen atom and the nitrogen atom does not have a substituent of R10, R11, R12, or R13.

2. An organic electroluminescence device, comprising:
a pair of electrodes; and
at least one organic layer interposed between the electrodes,
wherein the at least one organic layer comprises the compound of claim 1.

3. The device of claim 2, wherein the at least one organic layer is an electron-transporting layer.

4. The device of claim 2, wherein the at least one organic layer is a hole-blocking layer.

5. The device of claim 2, wherein the at least one organic layer is an emitting layer.

6. The device of claim 2, wherein the at least one organic layer is an electron-injecting layer.

7. The compound of claim 1, having a formula

8. The compound of claim 1, having a formula

9. The compound of claim 1, having a formula

10. The compound of claim 1, having a formula

11. The compound of claim 1, having a formula

12. The compound of claim 1, having a formula

13. The compound of claim 1, having a formula

14. The compound of claim 1, having a formula

15. The compound of claim 1, having a formula

16. The compound of claim 1, having a formula

17. The compound of claim 1, wherein R1 to R17 are independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group comprising 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted tetrakisphenyl group, a substituted or unsubstituted styryl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted pyrenyl group.

18. The compound of claim 1, wherein Ar is a phenyl group, a biphenyl group, a terphenyl group, a tetrakisphenyl group, a styryl group, a naphthyl group, an anthryl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a pyrimidyl group, a pyridoindolyl group, a furanyl group, a pyranyl group, a thiophenyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothiophenyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthyridinyl group, a phenanthrolinyl group, or an acridinyl group.

19. The compound of claim 1, wherein Ar is substituted or unsubstituted and is a phenyl or naphthyl group.

20. The compound of claim 1, wherein the substituted or unsubstituted aromatic hydrocarbon group is present for at least one of R6 to R9 and is a phenyl, biphenyl, terphenyl, tetrakisphenyl, styryl, naphthyl, fluorenyl, phenanthryl, indenyl, or pyrenyl.