CN104650076A - Compound containing imidazopyridine group and application thereof in organic electroluminescence - Google Patents

Compound containing imidazopyridine group and application thereof in organic electroluminescence Download PDF

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CN104650076A
CN104650076A CN201310728593.9A CN201310728593A CN104650076A CN 104650076 A CN104650076 A CN 104650076A CN 201310728593 A CN201310728593 A CN 201310728593A CN 104650076 A CN104650076 A CN 104650076A
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substituted
unsubstituted
phenyl
carbonatoms
compound containing
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李银奎
李艳蕊
范洪涛
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

The invention provides a novel organic compound having a structure as shown in a formula (I). In the compound, Ar is one of single bond, substituted or unsubstituted aromatic or hetero aromatic group of C6-C30, and substituted or unsubstituted condensed aromatic or condensed hetero aromatic group of C4-C30, and the number of substituent groups on Ar is 2-4; R1 and R2 are respectively and independently selected from H, substituted or unsubstituted aliphatic alkyl of C1-C12, substituted or unsubstituted aliphatic naphthenic base of C1-C12, and substituted or unsubstituted aryl or heterocyclic aryl of C6-C30; Ar1 is selected from substituted or unsubstituted aliphatic alkyl of C1-C12 or substituted or unsubstituted aryl of C6-C30; and n and m are respectively 1 or 2. The compound is stable in property and simple in preparation process, and can be used as a phosphorescence host material in an organic electroluminescence device to obtain relatively high luminescence efficiency and relatively low turn-on voltage.

Description

Compound containing imidazopyridine group and the application in organic electroluminescent
Technical field
The present invention relates to a kind of novel organic compound, and the application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device, through years of researches and development, have reached practical level, various material, such as hole material, electronic material, luminescent material, and display device technology of preparing has achieved considerable progress.Along with the requirement deeply with to material in practical process of research work, day by day obvious as the advantage of luminescent material with phosphorescence.The luminous efficiency of phosphor material, higher than fluorescent material 3 to 4 times, concerning many display products requiring brightness higher, is primary selection with phosphor material.Phosphorescence luminescent layer in device is steamed altogether by two class materials and is formed, and a class is material of main part, accounts for about 90% of common steaming component, and another kind of is phosphorescent coloring, accounts for about 10% of common steaming component.What tradition used is 4 at phosphorescent light body material, 4 '-N, N '-two carbazole biphenyl.This material has higher triplet, can mate well with phosphorescent coloring, but due to this material molecule amount less (molecular weight 484), make second-order transition temperature lower (Tg be about 1100C or once), in the easy crystallization of use procedure, form island, cause not bright spot, device lifetime shortens.The R and D of new phosphorescent light body material are operated in and constantly carry out, wherein there is the research patent (application number 200680047266.5 introduced by pyridyl in material structure, publication number CN101331626A), also the research patent (application number 200580014777.2 introduced by pyrimidyl in material structure is had, publication number CN1951155A), obtain good improvement effect all in various degree.
Therefore, based on existing research, the phosphorescent light body material of exploitation stability and high efficiency further, thus reduced bright voltage, improve device efficiency, there is very important actual application value.
Summary of the invention
The object of the invention is to propose a kind of novel organic compound, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field, especially, phosphorescent light body material is used as in organic luminescence function layer in organic electroluminescent device, and then it is low to obtain driving voltage, the organic electroluminescence device that current efficiency is high, the transformation period is longer.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
Organic compound provided by the invention contains imidazo [1, 2, a] pyridine groups and carbazole group, this kind of organic compound has higher molecular weight, be conducive to the raising of compound second-order transition temperature, simultaneously, imidazo [1, 2, a] pyridine groups and carbazole group directly can be connected to form compound, also phenylene can be passed through, biphenylene, phenenyl, the aromatic yl groups such as trivalent xenyl, or naphthyl, the fused ring aryl groups such as fluorenyl are connected, each group on this compound is in on-plane surface state, make whole molecule on space multistory, form distortion to a certain extent, the stereoeffect irregularity of molecule, be conducive to forming unformed film, particularly on the basis having carbazole group to exist, the present invention introduces imidazo ［ 1, 2, a ］ pyridine groups, effectively have adjusted the triplet (T of organic compound 1).When organic compound of the present invention is used for electroluminescent device as phosphorescence host time, electroluminescent improves significantly at everyways such as opening bright voltage, brightness, work-ing life.
The present invention discloses the compound that a class contains imidazopyridine group, and its general structure is as shown in the formula shown in (1):
Wherein:
Ar is selected from singly-bound, have substituted or unsubstituted aromatic ring group that carbonatoms is 6-30, have substituted or unsubstituted thick aromatic ring group that carbonatoms is 4-30, have substituted or unsubstituted heteroaromatic group that carbonatoms is 6-30, have carbonatoms is one in the substituted or unsubstituted thick heteroaromatic group of 4-30, and the substituting group number on group selected by Ar is two, three or four;
R 1and R 2separately be selected from H, substituted or unsubstituted heterocyclic aryl that substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12, carbonatoms are 6-30, carbonatoms are 6-30;
Ar 1be selected from the substituted or unsubstituted aryl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12 or carbonatoms are 6-30;
N≤2, m≤2, m and n is the integer being greater than zero.
Described Ar is directly connected on the pyridine ring of imidazopyridine group, works as R 1or R 2during for H, also by the R on imidazo ［ 1,2, a ］ pyridyl 1or R 2be connected with imidazo ［ 1,2, a ］ pyridine groups, that is Ar is connected directly between R on imidazo ［ 1,2, a ］ pyridyl 1or R 2position on.
Further, described R 1and R 2separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, carbazyl, (carbazole-9-base) phenyl, (carbazole-9-base) xenyl, carbazyl phenyl, carbazyl xenyl, phenyl replace carbazyl phenyl or N-phenyl carbazole base.
Further, described Ar 1be selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, naphthylphenyl.
Ar can be singly-bound, also can be replacement or unsubstituted divalence aromatic ring, trivalent aromatic ring, the tetravalence aromatic ring etc. of carbonatoms 6-30, preferably replace or unsubstituted phenylene, replacement or unsubstituted biphenylene, phenenyl, trivalent xenyl, tetravalence phenyl, tetravalence xenyl one of them.
Work as A rwhen not being singly-bound, A in general formula (1) rone preferably in following structure:
Work as R 1or R 2when not being H, R 1or R 2preferred one in following structure respectively:
In order to more clearly demonstrate content of the present invention, lower mask body describes the preferred structure of the compound that the present invention relates to:
The invention provides a kind of compound containing imidazopyridine group that can be applicable in organic electroluminescence device.
Further, the described compound containing imidazopyridine group is used as phosphorescent light body material in organic electroluminescence device.
Present invention also offers a kind of organic electroluminescence device, comprise substrate, and form anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, and the material of main part of described organic luminous layer is the compound containing imidazopyridine group described in one or more.
Further, in organic electroluminescence device, described luminescent layer is made up of material of main part and luminescent dye, and described luminescent dye is phosphorescent coloring.
The novel organic compound that the present invention develops, preparation technology is simple, easy and this material has good thermostability, has the molecular orbital(MO) and triplet (T that match with phosphorescent coloring 1), be good phosphorescent light body material in organic electroluminescence device.
Specific embodiment
Pyridine derivate used in the present invention, phenyl-bromide all can have been bought in Chemicals market at home for basic chemical industry raw materials such as aldehyde ketone, aryl boric acid derivative, carbazyl boric acid derivatives, all available common organic procedures synthesis of various condensed-nuclei aromatics bromo-derivative, condensed-nuclei aromatics boric acid derivatives.
Embodiment 1
The synthesis of following formula: compound
The first step,
2-amino-5-bromopyridine 0.892g(5mmol is added) in the flask of a 50ml, the bromo-2-phenyl acetophenone (6mmol) of 2-of 1.7g, sodium bicarbonate 0.491g(6mmol), Virahol 15ml, return stirring 12hrs, steam except Virahol, add 30ml Virahol and 60ml methylene dichloride, collect organic phase, use pillar layer separation product, sherwood oil and ethyl acetate drip washing, 3:1 proportioning.Obtain 1.17g, 67% productive rate, mp=198-1990C.
Second step,
At one 500 milliliters of there-necked flasks; join magnetic agitation, Ar gas shielded, add 2 of 14.9g; 3-phenylbenzene-6-bromine imidazo ［ 1; 2, a ］ THF of pyridine (molecular weight 348,0.0428mol) and 120ml; be chilled to-78 DEG C; drip the nBuLi(0.05mol of 25ml2M), temperature maintains-78 DEG C always, drips the B (OiPr) of 30ml after stirring 10min-78 DEG C time 3(0.153mol), stir and add dilute acid hydrolysis to room temperature, upper strata is white solid.Filter, separate solid product, water layer is neutralized to neutrality, and extract by ethyl acetate, extracting solution evaporate to dryness, adds diluted alkaline, and withdraw not molten impurity in alkali by ethyl acetate, water layer is neutralized to neutrality, and adularescent solid is separated out, and filters, obtains product.Be total to obtain 11.7g solid product, molecular weight 314, productive rate 86.46%.
3rd step,
1000 milliliters of there-necked flasks, join magnetic agitation, add 2,3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid 9.42g(molecular weight 314,0.03mol), 3,5-bis-(carbazole-9-base) bromobenzene 13.61(molecular weight 486,0.028mol), Pd (PPh 3) 4usage quantity 1.8g(molecular weight 1154,0.00155mol), sodium carbonate 175ml(2M), toluene 175ml, ethanol 175ml.After argon replaces, backflow, with TLC monitoring reaction, react completely after 3.5 hours, cooling, separated basic unit, evaporate to dryness, the ethyl acetate/petroleum ether with 1/10 carries out post separation, obtains 14.31g product, molecular weight 676, purity 98.5%, productive rate 74.5%.
Product MS(m/e): 676, ultimate analysis (C 49h 32n 4): theoretical value C:86.95%, H:4.77%, N:8.28%; Measured value C:86.91%, H:4.78%, N:8.31%.
Embodiment 2
The synthesis of compound 1
Building-up process divides work two step, and the first step is same as embodiment 1 the first step, just with 2-bromo-2-phenyl-1-(to bromophenyl) the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-makes raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, by 3,5-bis-(carbazole-9-base) bromobenzene changes 2-(into bromophenyl)-3-phenyl-6-bromine imidazo ［ 1,2, a ］ pyridine, other raw material and process constant, obtain compound 1.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.75%, H:4.84%, N:7.41%.
Embodiment 3
The synthesis of compound 2
Building-up process divides work two step, and the first step is same as embodiment 1 the first step, just with the bromo-2-(of 2-to bromophenyl) the bromo-2-phenyl acetophenone of methyl phenyl ketone replacement 2-makes raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, by 3,5-bis-(carbazole-9-base) bromobenzene changes 2-phenyl-3-(into bromophenyl)-6-bromine imidazo ［ 1,2, a ］ pyridine, other raw material and process constant, obtain compound 2.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.72%, H:4.86%, N:7.42%.
Embodiment 4
The synthesis of compound 3
Building-up process divides work two step, and the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-2-phenyl-1-() the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-makes raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 3.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.76%, H:4.83%, N:7.41%.
Embodiment 5
The synthesis of compound 4
Building-up process divides work two step, and the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-2-() the bromo-2-phenyl acetophenone of methyl phenyl ketone replacement 2-makes raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 4.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.72%, H:4.80%, N:7.48%.
Embodiment 6
The synthesis of compound 5
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just uses 2-bromo-2-phenyl-1-(to bromophenyl) the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-, 2-amino-4-bromopyridine replaces 2-amino-5-bromopyridine to make raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 5.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.73%, H:4.80%, N:7.47%.
Embodiment 7
The synthesis of compound 6
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just uses the bromo-2-(of 2-to bromophenyl) the bromo-2-phenyl acetophenone of methyl phenyl ketone replacement 2-, 2-amino-4-bromopyridine replaces 2-amino-5-bromopyridine to make raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 6.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.74%, H:4.85%, N:7.41%.
Embodiment 8
The synthesis of compound 7
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-2-phenyl-1-() the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-, 2-amino-4-bromopyridine replaces 2-amino-5-bromopyridine to make raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 7.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.73%, H:4.84%, N:7.43%.
Embodiment 9
The synthesis of compound 8
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-2-() the bromo-2-phenyl acetophenone of methyl phenyl ketone replacement 2-, 2-amino-4-bromopyridine replaces 2-amino-5-bromopyridine to make raw material, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 8.
Product MS(m/e): 752, ultimate analysis (C 55h 36n 4): theoretical value C:87.74%, H:4.82%, N:7.44%; Measured value C:87.76%, H:4.84%, N:7.40%.
Embodiment 10
The synthesis of compound 9
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just uses the bromo-1-(of 2-to bromophenyl) the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-, replace 2-amino-5-bromopyridine to make raw material with 2-amino-4-bromopyridine, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 9.
Product MS(m/e): 676, ultimate analysis (C 49h 32n 4): theoretical value C:86.95%, H:4.77%, N:8.28%; Measured value C:86.93%, H:4.76%, N:8.31%.
Embodiment 11
The synthesis of compound 10
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just uses the bromo-2-(of 2-to bromophenyl) the bromo-2-phenyl acetophenone of acetaldehyde replacement 2-, replace 2-amino-5-bromopyridine to make raw material with 2-amino-4-bromopyridine, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 10.
Product MS(m/e): 676, ultimate analysis (C 49h 32n 4): theoretical value C:86.95%, H:4.77%, N:8.28%; Measured value C:86.98%, H:4.75%, N:8.27%.
Embodiment 12
The synthesis of compound 11
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-1-() the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-, replace 2-amino-5-bromopyridine to make raw material with 2-amino-4-bromopyridine, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 11.
Product MS(m/e): 676, ultimate analysis (C 49h 32n 4): theoretical value C:86.95%, H:4.77%, N:8.28%; Measured value C:86.96%, H:4.74%, N:8.30%.
Embodiment 13
The synthesis of compound 12
Building-up process divides work two step, the first step is same as embodiment 1 the first step, just with bromophenyl between 2-bromo-2-() the bromo-2-phenyl acetophenone of acetaldehyde replacement 2-, replace 2-amino-5-bromopyridine to make raw material with 2-amino-4-bromopyridine, other raw material and process constant, obtain dibromo intermediate; The synthesis of second step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3 boric acid into, changes 3,5-bis-(carbazole-9-base) bromobenzene into synthesize dibromo intermediate here, other raw material and process constant, obtain compound 12.
Product MS(m/e): 676, ultimate analysis (C 49h 32n 4): theoretical value C:86.95%, H:4.77%, N:8.28%; Measured value C:86.96%, H:4.73%, N:8.31%.
Embodiment 14
The synthesis of compound 13
Building-up process divides work four step, the first step is same as embodiment 1 the first step, just uses the bromo-2-(of 2-to bromophenyl) the bromo-2-phenyl acetophenone of methyl phenyl ketone replacement 2-, replace 2-amino-5-bromopyridine to make raw material with PA, other raw material and process constant, obtain monobromo intermediate; The synthesis of second step is same as the second step of embodiment 1, just by 2,3-phenylbenzene-6-bromine imidazos ［ 1 wherein, 2, a ］ pyridine changes the monobromo intermediate that the first step here synthesizes into, other raw material and process constant, obtain 4-(2-phenylimidazole also ［ 1,2, a ］ pyridin-3-yl) phenylo boric acid; The synthesis of the 3rd step is same as the 3rd step of embodiment 1, just by 2,3-diphenyl-imidazoles wherein also ［ 1,2, a ］ pyridine-6-boric acid changes 4-(2-phenylimidazole also ［ 1,2, a ］ pyridin-3-yl that second step here synthesizes into) phenylo boric acid, by 3,5-bis-(carbazole-9-base) bromobenzene changes 1,3,5-tribromo-benzene into, other raw material and process constant, obtain dibromo intermediate; The synthesis of the 4th step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3-boric acid into, 3,5-bis-(carbazole-9-base) bromobenzene changed into the dibromo intermediate that the 3rd step here synthesizes, other raw material and process constant, obtain compound 13.
Product MS(m/e): 828, ultimate analysis (C 61h 40n 4): theoretical value C:88.38%, H:4.86%, N:6.76%; Measured value C:88.34%, H:4.85%, N:6.71%.
Embodiment 15
The synthesis of compound 14
Building-up process divides work four step, the first step is same as embodiment 1 the first step, just uses 2-bromo-2-phenyl-1-(to bromophenyl) the bromo-2-phenyl acetophenone of ethyl ketone replacement 2-, replace 2-amino-5-bromopyridine to make raw material with PA, other raw material and process constant, obtain monobromo intermediate; The synthesis of second step is same as the second step of embodiment 1, just by 2,3-phenylbenzene-6-bromine imidazos ［ 1 wherein, 2, a ］ pyridine changes the monobromo intermediate that the first step here synthesizes into, other raw material and process constant, obtain 4-(3-phenylimidazole also ［ 1,2, a ］ pyridine-2-base) phenylo boric acid; The synthesis of the 3rd step is same as the 3rd step of embodiment 1, just by 2,3-diphenyl-imidazoles wherein also ［ 1,2, a ］ pyridine-6-boric acid changes 4-(3-phenylimidazole also ［ 1,2, a ］ pyridine-2-base that second step here synthesizes into) phenylo boric acid, by 3,5-bis-(carbazole-9-base) bromobenzene changes 1,3,5-tribromo-benzene into, other raw material and process constant, obtain dibromo intermediate; The synthesis of the 4th step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3-boric acid into, 3,5-bis-(carbazole-9-base) bromobenzene changed into the dibromo intermediate that the 3rd step here synthesizes, other raw material and process constant, obtain compound 14.
Product MS(m/e): 828, ultimate analysis (C 61h 40n 4): theoretical value C:88.38%, H:4.86%, N:6.76%; Measured value C:88.36%, H:4.90%, N:6.74%.
Embodiment 16
The synthesis of compound 15
Building-up process divides work four step, and the first step is same as embodiment 1 the first step, just makes raw material with 2-amino-4-bromopyridine replacement 2-amino-5-bromopyridine, other raw material and process constant, obtain monobromo intermediate; The synthesis of second step is same as the second step of embodiment 1, just by 2,3-phenylbenzene-6-bromine imidazos ［ 1 wherein, 2, a ］ pyridine changes monobromo intermediate 2, the 3-phenylbenzene-7-bromine imidazo ［ 1,2 that the first step here synthesizes into, a ］ pyridine, other raw material and process constant, obtain 2,3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-7-phenylo boric acid; The synthesis of the 3rd step is same as the 3rd step of embodiment 1, just by 2,3-diphenyl-imidazoles wherein also ［ 1,2, a ］ pyridine-6-boric acid changes 2,3-diphenyl-imidazoles that second step here synthesizes also ［ 1 into, 2, a ］ pyridine-7-boric acid, change 3,5-bis-(carbazole-9-base) bromobenzene into 1,3,5-tribromo-benzene, other raw material and process constant, obtain dibromo intermediate; The synthesis of the 4th step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3-boric acid into, 3,5-bis-(carbazole-9-base) bromobenzene changed into the dibromo intermediate that the 3rd step here synthesizes, other raw material and process constant, obtain compound 15.
Product MS(m/e): 828, ultimate analysis (C 61h 40n 4): theoretical value C:88.38%, H:4.86%, N:6.76%; Measured value C:88.33%, H:4.87%, N:6.80%.
Embodiment 17
The synthesis of compound 16
Building-up process divides work four step, and the building-up process of the first step and second step and raw material are same as the first step and the second step of embodiment 1; The synthesis of the 3rd step is same as the 3rd step of embodiment 1, just changes 3,5-bis-(carbazole-9-base) bromobenzene into 1,3,5-tribromo-benzene, other raw material and process constant, obtain dibromo intermediate; The synthesis of the 4th step is same as the 3rd step of embodiment 1, just by 2 wherein, 3-diphenyl-imidazole also ［ 1,2, a ］ pyridine-6-boric acid changes N-phenyl carbazole-3-boric acid into, 3,5-bis-(carbazole-9-base) bromobenzene changed into the dibromo intermediate that the 3rd step here synthesizes, other raw material and process constant, obtain compound 16.
Product MS(m/e): 828, ultimate analysis (C 61h 40n 4): theoretical value C:88.38%, H:4.86%, N:6.76%; Measured value C:88.36%, H:4.85%, N:6.79%.
Here is the Application Example of the compounds of this invention:
Embodiment 18: the preparation of electroluminescent device and result
The preferred implementation of fabricate devices:
(1) device layout
Conveniently compare the performance of these materials, the present invention devises a simple electroluminescent device (substrate/anode/hole transmission layer (HTL)/phosphorescence host: phosphorescent coloring (EL)/electron transfer layer (ETL)/negative electrode), only use compound 1,7,9,13,16,17 as phosphorescent light body material illustration, CBP or NPB or mCP as phosphorescence host comparative material, Ir(ppy) 3, Ir (piq) 3with Firpic respectively as phosphorescent coloring.The structure of CBP and phosphorescent coloring is:
Substrate can use the substrate in conventional organic luminescence device, such as: glass or plastics.In element manufacturing of the present invention, select glass substrate, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group material.Hole mobile material selected in element manufacturing of the present invention is NPB.
Electron transport material selected in element manufacturing of the present invention is Bphen.
Negative electrode can adopt metal and composition thereof structure, as Mg:Ag, Ca:Ag etc., can be also electron injecting layer/metal-layer structure, as LiF/Al, Li 2the common cathode structures such as O/Al.Electron injection material selected in element manufacturing of the present invention is LiF, and cathode material is Al.
(2) element manufacturing
Sheet glass supersound process in commercial detergent of ITO transparency conducting layer will be coated with; rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely; by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10 -5~ 9 × 10 -3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
On hole transmission layer, vacuum evaporation phosphorescent light body material 1,7,9,13,16,17 of the present invention is total to evaporation phosphorescent coloring Ir(ppy simultaneously) 3(or Firpic, or Ir(piq) 3), phosphorescent light body material also can replace with CBP or NPB or mCP.Evaporation is as the luminescent layer of device altogether for phosphorescence host and dyestuff, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm, luminescent dye Ir(ppy) 3doping content be the doping content of 10%, FIrpic be 12%, Ir(piq) 3doping content be 5%, doping content mentioned here refers to that the evaporation rate ratio of luminescent dye and material of main part is 10:100,12:100,5:100;
On luminescent layer, vacuum evaporation one deck compd B phen is as the electron transfer layer of device, and its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
At the upper vacuum evaporation LiF of electron transfer layer (ETL) as electron injecting layer, thickness 0.5nm.On LiF layer, evaporating Al layer is as the negative electrode of device, and thickness is 150nm.
Device performance sees the following form (device architecture: ITO/NPB(40nm)/phosphorescence host: phosphorescent coloring (30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm))
Luminescent layer Require brightness cd/m 2 Voltage V Current density A/m 2 Current efficiency cd/A Glow color
CBP:Ir(ppy) 3 1000 4.1 30.95 32.3 Green glow
1:Ir(ppy) 3 1000 3.8 26.17 38.2 Green glow
7:Ir(ppy) 3 1000 3.8 26.38 37.9 Green glow
9:Ir(ppy) 3 1000 3.7 26.59 37.6 Green glow
mCP:FIrpic 1000 4.7 69.93 14.3 Blue light
13:FIrpic 1000 4.5 65.78 15.2 Blue light
16:FIrpic 1000 4.4 64.51 15.5 Blue light
NPB:Ir(piq) 3 1000 4.5 138.88 7.2 Ruddiness
17:Ir(piq) 3 1000 4.3 119.04 8.4 Ruddiness
Above result shows, new organic materials of the present invention is used for organic electroluminescence device, can effectively reduce landing voltage, and improving current efficiency, is phosphorescence host of good performance.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.

Claims (11)

1. the compound containing imidazopyridine group, is characterized in that having structure as the formula (1):
Wherein:
Ar is selected from singly-bound, have substituted or unsubstituted aromatic ring group that carbonatoms is 6-30, have substituted or unsubstituted thick aromatic ring group that carbonatoms is 4-30, have substituted or unsubstituted heteroaromatic group that carbonatoms is 6-30, have carbonatoms is one in the substituted or unsubstituted thick heteroaromatic group of 4-30, and the substituting group number on group selected by Ar is two, three or four;
R 1and R 2separately be selected from H, substituted or unsubstituted heterocyclic aryl that substituted or unsubstituted aryl that substituted or unsubstituted aliphatics cycloalkyl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12, carbonatoms are 1-12, carbonatoms are 6-30, carbonatoms are 6-30;
Ar 1be selected from the substituted or unsubstituted aryl that substituted or unsubstituted aliphatic alkyl that carbonatoms is 1-12 or carbonatoms are 6-30;
N≤2, m≤2, m and n is the integer being greater than zero.
2. the compound containing imidazopyridine group according to claim 1, is characterized in that, Ar base directly and the connection of imidazo ［ 1,2, a ］ pyridine groups, or, work as R 1or R 2during for H, Ar base passes through R 1or R 2be connected with imidazo ［ 1,2, a ］ pyridine groups.
3. the compound containing imidazopyridine group according to claim 1, is characterized in that, described R 1and R 2separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, carbazyl, (carbazole-9-base) phenyl, (carbazole-9-base) xenyl, carbazyl phenyl, carbazyl xenyl, phenyl replace carbazyl phenyl or N-phenyl carbazole base.
4. the compound containing imidazopyridine group according to claim 1, is characterized in that, described Ar 1be selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, naphthylphenyl.
5. the compound containing imidazopyridine group according to claim 1, it is characterized in that, when Ar is not singly-bound, the preferred structure formula of Ar is selected from the one in following structure:
6. the compound containing imidazopyridine group according to claim 1, is characterized in that, work as R 1or R 2when not being H, R 1or R 2preferred structure formula be independently selected from one in following structure:
7. the compound containing imidazopyridine group according to claim 1, it is characterized in that, described organic compound is preferably from following structural formula:
8. the compound containing imidazopyridine group described in any one of claim 1-7, is applied in organic electroluminescence device.
9. a kind of compound containing imidazopyridine group being applied to organic electroluminescence device according to claim 8, is characterized in that, can be used as phosphorescent light body material.
10. an organic electroluminescence device, comprises substrate, and forms anode layer, organic luminescence function layer and cathode layer on the substrate successively; Described organic luminescence function layer comprises hole transmission layer, organic luminous layer and electron transfer layer, it is characterized in that:
The material of main part of described organic luminous layer is one or more compounds containing imidazopyridine group according to any one of claim 1-7.
11. a kind of organic electroluminescence devices according to claim 10, it is characterized in that, described luminescent layer is made up of material of main part and luminescent dye, and described luminescent dye is phosphorescent coloring.
CN201310728593.9A 2013-12-26 2013-12-26 Compound containing imidazopyridine group and application thereof in organic electroluminescence Pending CN104650076A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108864091A (en) * 2018-09-03 2018-11-23 上海道亦化工科技有限公司 A kind of imidazopyridine derivatives and application thereof and luminescent device
JP2019505478A (en) * 2015-12-08 2019-02-28 ヒソン・マテリアル・リミテッドＨｅｅｓｕｎｇ Ｍａｔｅｒｉａｌ Ｌｔｄ． Heterocyclic compound and organic light emitting device using the same
CN109638171A (en) * 2017-12-22 2019-04-16 广州华睿光电材料有限公司 Organic mixture, high polymer, composition and application thereof
CN110357882A (en) * 2019-07-17 2019-10-22 深圳市华星光电半导体显示技术有限公司 Nitrogenous heterocyclic organic compound and organic electroluminescence device
CN112574254A (en) * 2020-09-25 2021-03-30 上海和辉光电股份有限公司 Compound for organic luminescence and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012049518A (en) * 2010-07-27 2012-03-08 Konica Minolta Holdings Inc Material for organic electroluminescent element, compound, organic electroluminescent element, display device, and luminaire
CN102858912A (en) * 2010-04-23 2013-01-02 第一毛织株式会社 Compound for optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode
WO2013183851A1 (en) * 2012-06-04 2013-12-12 (주)피엔에이치테크 Novel organic electroluminescent element compound and organic electroluminescent element comprising same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102858912A (en) * 2010-04-23 2013-01-02 第一毛织株式会社 Compound for optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode
JP2012049518A (en) * 2010-07-27 2012-03-08 Konica Minolta Holdings Inc Material for organic electroluminescent element, compound, organic electroluminescent element, display device, and luminaire
WO2013183851A1 (en) * 2012-06-04 2013-12-12 (주)피엔에이치테크 Novel organic electroluminescent element compound and organic electroluminescent element comprising same

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019505478A (en) * 2015-12-08 2019-02-28 ヒソン・マテリアル・リミテッドＨｅｅｓｕｎｇ Ｍａｔｅｒｉａｌ Ｌｔｄ． Heterocyclic compound and organic light emitting device using the same
EP3392246A4 (en) * 2015-12-08 2019-10-30 Heesung Material Ltd. Heterocyclic compound and organic light emitting element using same
CN109638171A (en) * 2017-12-22 2019-04-16 广州华睿光电材料有限公司 Organic mixture, high polymer, composition and application thereof
CN109638171B (en) * 2017-12-22 2020-10-23 广州华睿光电材料有限公司 Organic mixtures, polymers, compositions and uses thereof
CN108864091A (en) * 2018-09-03 2018-11-23 上海道亦化工科技有限公司 A kind of imidazopyridine derivatives and application thereof and luminescent device
CN110357882A (en) * 2019-07-17 2019-10-22 深圳市华星光电半导体显示技术有限公司 Nitrogenous heterocyclic organic compound and organic electroluminescence device
CN112574254A (en) * 2020-09-25 2021-03-30 上海和辉光电股份有限公司 Compound for organic luminescence and application thereof
CN112574254B (en) * 2020-09-25 2023-03-07 上海和辉光电股份有限公司 Compound for organic luminescence and application thereof

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