CN104650088B - A kind of derivative of carbazolyl-containing and its application in organic electroluminescence device - Google Patents

A kind of derivative of carbazolyl-containing and its application in organic electroluminescence device Download PDF

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CN104650088B
CN104650088B CN201310728615.1A CN201310728615A CN104650088B CN 104650088 B CN104650088 B CN 104650088B CN 201310728615 A CN201310728615 A CN 201310728615A CN 104650088 B CN104650088 B CN 104650088B
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carbazolyl
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CN104650088A (en
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李银奎
汤金明
范洪涛
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Guan Eternal Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—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
    • 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

Have the invention provides one kind such as formula（1）、（2）Or（3）The derivative of shown structure novel carbazolyl-containing：Wherein：One of A and B are N, and another H in CH groups or CH groups is by C1 12 alkyl, C6 30 aryl, CF3、‑SCH3In a kind of substituted group；Ar is selected from one of singly-bound, phenylene, tri-substituted phenyl, tetra-substituted phenyl, biphenylene, three substituted biphenyl bases；R1And R2Separately it is selected from H, C1 12 aliphatic alkyl, C1 12 aliphatic cycloalkyl, C6 30 aryl, C6 30 heterocyclic aryl, methyl mercapto, methoxyl group, ethyoxyl or trifluoromethyl；R3And R4It is independently selected from C1 12 aliphatic alkyl or C6 30 aryl；R3Can also be H；N is 1 or 2.Such compound property is stable, and preparation technology is simple, and phosphorescent light body material can be used as in organic electroluminescence device, obtains higher luminous efficiency and relatively low opens bright voltage.

Description

A kind of derivative of carbazolyl-containing and its application in organic electroluminescence device
Technical field
The present invention relates to a kind of novel organic compound, and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device pass through years of researches and development, have reached practical level, various materials, Such as hole material, electronic material, luminescent material, display device technology of preparing has been achieved for considerable progress.With research Work deeply and it is practical during requirement to material, it is increasingly obvious as the advantage of luminescent material with phosphorescence.Phosphorescence material The luminous efficiency of material is higher than 3 to 4 times of fluorescent material, for many display products for requiring that brightness is higher, is with phosphor material Primary selection.Phosphorescence luminescent layer in device is steamed altogether by two class materials to be formed, and a class is material of main part, accounts for the 90% of common steaming component Left and right, another kind of is phosphorescent coloring, accounts for 10% or so of common steaming component.What tradition was used is 4 in phosphorescent light body material, 4 '-N, The carbazole biphenyls of N '-two.The material has higher triplet, can be well matched with phosphorescent coloring, but due to the material point Son amount is smaller（Molecular weight 484）So that glass transition temperature is relatively low（Tg about 1100C or once）, easily crystallized using process, shape Into island, cause not bright spot, device lifetime shortens.R and D to new phosphorescent light body material are operated in continuous progress, its In have the research patent that pyridine radicals is introduced into material structure（Application number 200680047266.5, publication number CN101331626A）, also there is the research patent that pyrimidine radicals is introduced into material structure（Application number 200580014777.2, it is open Number CN1951155A）, preferable improvement effect is all obtained in various degree.
Therefore, based on existing research, the phosphorescent light body material of stability and high efficiency is further developed, so as to reduce bright electricity Pressure, improves device efficiency, with critically important actual application value.
The content of the invention
The purpose of the present invention is to propose to a kind of new organic compound, such compound can be used for organic electroluminescent Display field, especially, is used as phosphorescent light body material, and then obtain in the organic luminescence function layer in organic electroluminescent device Driving voltage is low, the organic electroluminescence device that current efficiency is high, half-life period is longer.
Compound proposed by the present invention contains imidazo ［ 1,2-a ］ pyrimidine group and carbazole group, or containing imidazo 1, 2-a ］ pyrazine group and carbazole group, this kind of organic compound has higher molecular weight, is conducive to compound glass transition temperature Raising, meanwhile, imidazo ［ 1,2-a ］ pyrimidine group or imidazo ［ 1,2-a ］ pyrazine group and carbazole group can directly connect Connect to form compound, can also by aromatic yl groups such as phenylene, biphenylene, phenenyl, trivalent xenyls, or naphthyl, The fused ring aryl group such as fluorenyl is connected, and each group in the compound is in on-plane surface state so that whole molecule is in space Distortion to a certain extent is formed in solid, the stereoeffect of molecule is irregular, advantageously forms unformed film, particularly On the basis of with the presence of carbazyl, present invention introduces imidazo ［ 1,2-a ］ pyrimidine group or imidazo ［ 1,2-a ］ pyrazinyl Group, effectively have adjusted the triplet of material（T1）.When using the present invention material as phosphorescence host be used for electroluminescent When device, electroluminescent improves significantly opening the everyways such as bright voltage, brightness, service life.
Therefore, having the invention provides one kind such as formula（1）、（2）Or（3）The derivative of the carbazolyl-containing of shown structure Thing：
Wherein：
One of A and B are N, and another is that H in CH groups or CH groups is 6-30 by C1-12 alkyl, carbon number Aryl, carbon number be 6-30 heterocyclic aryl ,-CF3、-SCH3In a kind of substituted group；
Ar be selected from singly-bound, phenylene, tri-substituted phenyl, tetra-substituted phenyl, biphenylene, three substituted biphenyl bases wherein it One；
R1And R2Separately selected from H, substituted or unsubstituted aliphatic alkyl, the carbon atom that carbon number is 1-12 Substituted or unsubstituted aryl that substituted or unsubstituted aliphatic cycloalkyl that number is 1-12, carbon number are 6-30, carbon are former Subnumber is 6-30 substituted or unsubstituted aryl, methyl mercapto, methoxyl group, ethyoxyl or trifluoromethyl；
R3The substituted or unsubstituted aliphatic alkyl or carbon number for being 1-12 selected from H, carbon number are taking for 6-30 Generation or unsubstituted aryl；
R4The substitution that the substituted or unsubstituted aliphatic alkyl or carbon number for being 1-12 selected from carbon number are 6-30 Or unsubstituted aryl；
N is 1 or 2.
Further, Ar can directly and imidazo ［ 1,2-a ］ pyrimidine group or imidazo ［ 1,2-a ］ pyrazine group connection, Or, work as R1Or R2During for H, Ar passes through R1Or R2With imidazo ［ 1,2-a ］ pyrimidine group or imidazo ［ 1,2-a ］ pyrazine group It is connected, is also just to say that Ar is connected directly between R1Or R2Position on；
Further, the R1And R2Separately selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, just oneself Base, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, carbazyl, carbazyl phenyl, carbazyl phenyl, the fluorenes of phenyl substitution Base, N- fluorenyls carbazyl, methyl mercapto, methoxyl group, ethyoxyl or trifluoromethyl.
Further, the R3Selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, Ethylbenzene or xenyl.
Further, the R4Selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, second Phenyl, xenyl or naphthyl.
Formula（1）、（2）Or（3）In, when Ar is not singly-bound, Ar skeleton structure preferably is selected from following structures：
Further, in formula（1）、（2）Or（3）In, one of A and B are N, another in CH groups or CH groups H by methyl, ethyl, propyl group, normal-butyl, n-pentyl ,-CF3、-SCH3, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, click The monobasic group of oxazolyl, N- phenyl carbazole bases.
Work as R1Or R2When being not H, the R1Or R2It may be selected from following any structures：
In order to become apparent from illustrating present invention, the narration of lower mask body the present invention relates to compound preferred structure：
The invention provides a kind of derivative for the carbazolyl-containing that can be applied in organic electroluminescence device.
Further, the derivative of described carbazolyl-containing can be used as phosphorescence host material in organic electroluminescence device Material.
Present invention also offers a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, organic luminescence function layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer And electron transfer layer, the material of main part of the organic luminous layer is the derivative of the carbazolyl-containing described in one or more.
Further, in organic electroluminescence device, the luminescent layer is made up of material of main part and luminescent dye, described Luminescent dye is phosphorescent coloring.
The derivative for the new carbazolyl-containing that the present invention is developed, preparation technology is simple, easy and the material has well Heat endurance, have the molecular orbit matched with phosphorescent coloring and triplet（T1）, in organic electroluminescence device It is good phosphorescent light body material.
Brief description of the drawings
In order that present disclosure is more easily understood, below according to specific embodiment of the invention and with reference to accompanying drawing, The present invention is further detailed explanation；Try to achieve the highest occupied molecular of compound respectively with Gaussian03/6-31 methods Track（HOMO）, lowest unoccupied molecular orbital（LUMO）And triplet（T1）.Wherein：
Fig. 1 is the highest occupied molecular orbital(HOMO) of organic compound 4 of the present invention, and HOMO energy levels are -5.085ev, three Line state energy level T1=2.3418ev；
Fig. 2 is the lowest unoccupied molecular orbital of organic compound 4 of the present invention, and lumo energy is -1.402ev.
Specific embodiment
Example 1 below-embodiment 15 is the synthetic example of the application：
Various imidazos [1,2-a] pyrimidine halo derivatives and imidazo [1,2-A] pyrazine halo used in the present invention Derivative, for example, 5,7- dichloro-imidazoles simultaneously [1,2-a] pyrimidine, 6- bromines imidazo [1,2-a] pyrimidine, 3- bromines imidazo [1,2-a] Pyrimidine, 7- chloro- 5- (methyl mercapto) imidazo [1,2-c] pyrimidine, bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, 2- (3- bromophenyls) Imidazoles [1,2-a] and pyrimidine, the chloro- 2-p- tolylimidazols [1,2-a] of 6- and pyrimidine, 2- (4- bromophenyls)-imidazo [1,2- A] -7- methylpyrimidines, 2- (3- bromophenyls)-imidazo [1,2-a] pyrimidine, 2- (3- bromophenyls)-imidazo [1,2-a] -7- first Yl pyrimidines, 2- (4- bromophenyls)-imidazo [1,2-a] pyrimidine, 3- bromo- 7- (trifluoromethyl) imidazo [1,2-a] pyrimidine, 6- bromines Imidazo [1,2-A] pyrazine, bromo- 8- chlorine imidazo [1, the 2-A] pyrazines of 3-, 6,8- bis- bromo- imidazoles [1,2-A] pyrazines, the chloro- miaows of 5- Azoles simultaneously [1,2-A] pyrazine, 8- chlorine imidazo [1,2-a] pyrazine, 3- bromines imidazo [1,2-a] pyrazine, 2- bromines imidazo [1,2-a] Pyrazine, can chemical industry at home etc., commercially available at home, the chemical raw material such as various aryl boric acid and its Knit-the-brows alcohol esters Conveniently buy in product market；Some special aryl boric acid derivatives and intermediate can use common organic procedures to synthesize.
Embodiment 1
The synthesis of compound 1
The first step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3- 7.86g（Molecular weight 231,0.034mol）, phenyl boric acid Knit-the-brows alcohol esters 7.14g（Molecular weight 204,0.035mol）, catalyst Pd (PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 300ml, ethanol 150ml.It is stirred at reflux, is monitored and reacted with TLC, reacts complete after reaction 1.5hs.Cooling, separates, is evaporated, use column chromatography methods Separation product, eluent uses 1：4 ethyl acetate：Petroleum ether, obtains 7.46g faint yellow solid compounds, purity 96.0%, production Rate：92.0%.
Second step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar gas shieldeds add 3- phenyl -6- chlorine imidazos [1,2-a] phonetic Pyridine 7.16g（Molecular weight 229,0.030mol）, to bromobenzeneboronic acid Knit-the-brows alcohol esters 9.1g（Molecular weight 282,0.032mol）, catalyst Pd(PPh3)4Consumption 1.8g（Molecular weight 1154,0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 300ml, ethanol 150ml.It is stirred at reflux, is monitored and reacted with TLC, reacts complete after reaction 3.5hs.Cooling, separates, is evaporated, use column chromatography methods Separation product, eluent uses 1：3 ethyl acetate：Petroleum ether, obtains 9.0g faint yellow solid compounds, purity 97.0%, production Rate：83.2%.
3rd step,
In the there-necked flask of a 2000ml, with mechanical agitation, Ar gas shieldeds.Add 3,5- bis-（Carbazole -9- bases）Bromobenzene 9.72g （Molecular weight 486,0.02mol）, connection pinacol borate 5.6g（Molecular weight 254.2,0.022mol）, Pd (dppf) Cl23.2g （0.0044mol）, potassium acetate 36g（Molecular weight 138,0.26mol）, Isosorbide-5-Nitrae dioxane 500ml.Mechanical agitation is started, in decompression Under the conditions of ventilation 3 times after keep Ar gas shieldeds, use TLC（Thin-layer chromatography）Monitoring reaction, untill raw material is wholly absent, backflow 3 After hour, reaction is complete.Let cool, reaction system is allocated as two layers, separates organic layer, is evaporated, obtain 9.72g products, yield 91.0%。
4th step,
In the there-necked flask of a 1000ml, with mechanical agitation, Ar protections add -6- pairs of the 3- phenyl of second step generation above Bromophenyl imidazo [1,2-a] pyrimidine 7.2g（Molecular weight 349, purity 97%, 0.02mol）, 3,5- bis-（Carbazole -9- bases）Benzene boron Sour Knit-the-brows alcohol esters 11.8g（Molecular weight 534,0.022mol）, catalyst Pd (PPh3)4Consumption 1.8g（Molecular weight 1154, 0.001556mol）, aqueous sodium carbonate 120ml（2M）, toluene 300ml, ethanol 150ml.It is stirred at reflux, monitors anti-with TLC Should, reacted after coreaction 3.5hs complete.Cooling, separates, is evaporated, use column chromatography methods separation product, eluent uses 1：1 second Acetoacetic ester：Petroleum ether, obtains 11.76g faint yellow solid compounds, purity 99.0%, yield：86.0%.
Product MS（m/e）：677, elementary analysis（C48H31N5）：Theoretical value C：85.06%, H：4..61%, N：10.33%； Measured value C：85.03%, H：4..65%, N：10.32%.
Embodiment 2
The synthesis of compound 1
Building-up process is same as the first step of embodiment 1, is simply replaced with 6,9- diphenyl carbazole -3- phenyl boric acid Knit-the-brows alcohol esters Phenyl boric acid Knit-the-brows alcohol esters make raw material, and other raw materials and process are constant, obtain compound 1.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4.68%, N：9.29%；It is real Measured value C：86.05%, H：4.70%, N：9.25%.
Embodiment 3
The synthesis of compound 2
Building-up process is same as the first step of embodiment 1, simply replaces phenyl boric acid with 9- phenyl carbazole -3- boric acid Knit-the-brows alcohol esters Knit-the-brows alcohol esters, with 5,7- dichloro-imidazoles, simultaneously [1,2-a] pyrimidine makees raw material instead of bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, other Raw material and process are constant, obtain compound 2.
Product MS（m/e）：601, elementary analysis（C42H27N5）：Theoretical value C：83.84%, H：4.52%, N：11.64%； Measured value C：83.85%, H：4.54%, N：11.61%.
Embodiment 4
The synthesis of compound 3
Building-up process is same as the first step of embodiment 1, simply replaces benzene with 6,9- diphenyl carbazole -3- boric acid Knit-the-brows alcohol esters Boric acid Knit-the-brows alcohol esters, with 5,7- dichloro-imidazoles, simultaneously [1,2-a] pyrimidine makees raw material instead of bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, Other raw materials and process are constant, obtain compound 3.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4.68%, N：9.29%；It is real Measured value C：86.06%, H：4.65%, N：9.29%.
Embodiment 5
The synthesis of compound 4
Building-up process is same as the first step of embodiment 1, simply replaces phenyl boric acid with 9- phenyl carbazole -3- boric acid Knit-the-brows alcohol esters Knit-the-brows alcohol esters, raw material is made with 6,8- dibromos imidazo [1,2-a] pyrazine instead of bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, other Raw material and process are constant, obtain compound 4.
Product MS（m/e）：601, elementary analysis（C42H27N5）：Theoretical value C：83.84%, H：4.52%, N：11.64%； Measured value C：83.81%, H：4.50%, N：11.69%.
Embodiment 6
The synthesis of compound 5
Building-up process is same as the first step of embodiment 1, simply replaces benzene with 6,9- diphenyl carbazole -3- boric acid Knit-the-brows alcohol esters Boric acid Knit-the-brows alcohol esters, raw material is made with 6,8- dibromos imidazo [1,2-a] pyrazine instead of bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, Other raw materials and process are constant, obtain compound 5.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4.68%, N：9.29%；It is real Measured value C：86.05%, H：4.65%, N：9.30%.
Embodiment 7
The synthesis of compound 6
Building-up process is same as the first step of embodiment 1, simply replaces phenyl boric acid with 9- phenyl carbazole -3- boric acid Knit-the-brows alcohol esters Knit-the-brows alcohol esters, raw material is made with bromo- 8- chlorine imidazo [1, the 2-a] pyrazines of 3- instead of bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, its Its raw material and process are constant, obtain compound 6.
Product MS（m/e）：601, elementary analysis（C42H27N5）：Theoretical value C：83.84%, H：4.52%, N：11.64%； Measured value C：83.81%, H：4.49%, N：11.70%.
Embodiment 8
The synthesis of compound 7
Building-up process is same as the first step of embodiment 1, simply replaces benzene with 6,9- diphenyl carbazole -3- boric acid Knit-the-brows alcohol esters Boric acid Knit-the-brows alcohol esters, replace bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3- to make former with bromo- 8- chlorine imidazo [1, the 2-a] pyrazines of 3- Material, other raw materials and process are constant, obtain compound 7.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4.68%, N：9.29%；It is real Measured value C：86.04%, H：4.64%, N：9.32%.
Embodiment 9
The synthesis of compound 8
The first step,
In the there-necked flask of a 2000ml, with mechanical agitation, Ar gas shieldeds.Add 3,5- bis-（9- phenyl carbazole -3- bases）Bromine Benzene 12.76g（Molecular weight 638,0.02mol）, connection pinacol borate 5.6g（Molecular weight 254.2,0.022mol）, Pd (dppf) Cl23.2g（0.0044mol）, potassium acetate 36g（Molecular weight 138,0.26mol）, Isosorbide-5-Nitrae dioxane 500ml.Machinery is started to stir Mix, keep Ar gas shieldeds after taking a breath 3 times at reduced pressure conditions, use TLC（Thin-layer chromatography）Monitoring reaction, to raw material be wholly absent for Only, after flowing back 3 hours, reaction is complete.Let cool, reaction system is allocated as two layers, separates organic layer, is evaporated, obtain 12.1g products, Yield 88.1%.
Second step reaction is same as the step of embodiment 1 the 4th, simply by 3- phenyl -6- p-bromophenyls imidazo [1,2-a] pyrimidine Replaced with 3- phenyl -6- chlorine imidazo [1,2-a] pyrimidine, 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters 3,5- bis-（9- Phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain compound 8.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4..68%, N：9.29%； Measured value C：86.06%, H：4..70%, N：9.24%.
Embodiment 10
The synthesis of compound 9
Building-up process is allocated as two steps.The first step is same as the step of embodiment 1 the 4th, simply by 3- phenyl -6- p-bromophenyl imidazoles And [1,2-a] pyrimidine is replaced with bromo- 6- chlorine imidazo [1, the 2-a] pyrimidines of 3-, 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters With 3,5- bis-（9- phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain a chlorine Intermediate；Second step is same as the first step of embodiment 1, and the chloro thing simply synthesized with the first step here replaces the bromo- 6- chlorine of 3- Imidazo [1,2-a] pyrimidine makees raw material, and other raw materials and process are constant, obtain compound 9.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4..68%, N：9.29%； Measured value C：86.05%, H：4..72%, N：9.23%.
Embodiment 11
The synthesis of compound 10
Building-up process is same as the step of embodiment 1 the 4th, simply uses 3- phenyl -6- p-bromophenyls imidazo [1,2-a] pyrimidine 2- p-methylphenyls -6- chlorine imidazo [1,2-a] pyrimidine is replaced, and 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters 3,5- bis- （9- phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain compound 10.
Product MS（m/e）：767, elementary analysis（C55H37N5）：Theoretical value C：86.02%, H：4.86%, N：9.12%；It is real Measured value C：86.05%, H：4.88%, N：9.07%.
Embodiment 12
The synthesis of compound 11
Building-up process is same as the step of embodiment 1 the 4th, simply uses 3- phenyl -6- p-bromophenyls imidazo [1,2-a] pyrimidine 3- phenyl -8- chlorine imidazo [1,2-a] pyrazine is replaced, and 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters 3,5- bis-（9- benzene Base carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain compound 11.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4..68%, N：9.29%； Measured value C：86.01%, H：4..65%, N：9.34%.
Embodiment 13
The synthesis of compound 12
Building-up process is allocated as two steps.The first step is same as the step of embodiment 1 the 4th, simply by 3- phenyl -6- p-bromophenyl imidazoles And [1,2-a] pyrimidine is replaced with bromo- 8- chlorine imidazo [1, the 2-a] pyrazines of 3-, 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters With 3,5- bis-（9- phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain a chlorine Intermediate；Second step is same as the first step of embodiment 1, and the chloro thing simply synthesized with the first step here replaces the bromo- 6- chlorine of 3- Imidazo [1,2-a] pyrimidine makees raw material, and other raw materials and process are constant, obtain compound 12.
Product MS（m/e）：753, elementary analysis（C54H35N5）：Theoretical value C：86.03%, H：4..68%, N：9.29%； Measured value C：86.07%, H：4..67%, N：9.26%.
Embodiment 14
The synthesis of compound 13
Building-up process is same as the step of embodiment 1 the 4th, simply uses 3- phenyl -6- p-bromophenyls imidazo [1,2-a] pyrimidine Simultaneously [1,2-a] pyrimidine is replaced the bromo- 7- trifluoromethyl imidazoles of 3-, and 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters 3,5- bis- （9- phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain compound 13.
Product MS（m/e）：745, elementary analysis（C49H30F3N5）：Theoretical value C：78.91%, H：4.05%, F：7.64, N： 9.40%；Measured value C：78.94%, H：4.03%, F：7.67, N：9.36%.
Embodiment 15
The synthesis of compound 14
Building-up process is same as the step of embodiment 1 the 4th, simply uses 3- phenyl -6- p-bromophenyls imidazo [1,2-a] pyrimidine 5- methyl mercaptos -7- chlorine imidazo [1,2-a] pyrimidine is replaced, and 3,5- bis-（Carbazole -9- bases）Phenyl boric acid Knit-the-brows alcohol esters 3,5- bis-（9- Phenyl carbazole -3- bases）Phenyl boric acid Knit-the-brows alcohol esters replace making raw material, and other raw materials and process are constant, obtain compound 14.
Product MS（m/e）：723, elementary analysis（C49H33N5S）：Theoretical value C：81.30%, H：4.59%, S：4.43%, N： 9.67%；Measured value C：81.33%, H：4.62%, S：4.41%, N：9.64%.
Here is the Application Example of the compounds of this invention：
Embodiment 16：The preparation of electroluminescent device and result
Prepare the preferred embodiment of device：
（1）Device is designed
Compare the performance of these materials for convenience, the present invention devises a simple electroluminescence device（Substrate/anode/sky Cave implanted layer（HIL）/ hole transmission layer（HTL）/ phosphorescence host（HOST）:Phosphorescent coloring (Dopant)/electron transfer layer (ETL)/electron injecting layer（EIL）/ negative electrode）, using only compound 1,4,5,7,8,10,13 as phosphorescent light body material illustration, CBP compares material, Ir as phosphorescence host（ppy）3It is used as phosphorescent coloring.The structure of CBP and phosphorescent coloring is：
Substrate can use the substrate in conventional organic luminescence device, for example：Glass or plastics.In the device system of the present invention Glass substrate is selected in work, ITO makees anode material.
Hole injection layer selects 2-TNATA.
Hole transmission layer can use various tri-arylamine group materials.Selected hole is passed in the element manufacturing of the present invention Defeated material is NPB.
Selected electron transport material is Bphen in the element manufacturing of the present invention.
Wherein 2-TNATA, NPB, Bphen structural formula is respectively：
Negative electrode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc. or electron injecting layer/gold Belong to Rotating fields, such as LiF/Al, Li2The common cathode structure such as O.The selected electron injection material in the element manufacturing of the present invention It is LiF, cathode material is Al.
（2）Element manufacturing
The glass plate of transparent conductive layer will be coated with ultrasonically treated in commercial detergent, rinsed in deionized water, In acetone：Ultrasonic oil removing in alcohol mixed solvent, is baked under clean environment and removes moisture content completely, clear with ultraviolet light and ozone Wash, and with low energy cation beam bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10 is evacuated to-5~9 × 10-4Pa, above-mentioned Vacuum evaporation 2-TNATA is as hole injection layer on anode tunic, and evaporation rate is 0.1nm/s, and evaporation thickness is 20nm；In sky Vacuum evaporation NPB is as hole transmission layer on the implanted layer of cave, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm；
Phosphorescent light body material 1,4,5,7,8,10,13 using the double source vacuum evaporation present invention on hole transmission layer is same When phosphorescent coloring Ir is deposited altogether（ppy）3, phosphorescent light body material can also replace with CBP.Phosphorescence host and dyestuff are deposited as device altogether The luminescent layer of part, evaporation rate is 0.1nm/s, and the speed of phosphorescent coloring is 0.015nm/S, and evaporation total film thickness is 30nm；
The stratification compound Bphen of vacuum evaporation one is as the electron transfer layer of device on luminescent layer, and its evaporation rate is 0.1nm/s, evaporation total film thickness is 20nm；
In electron transfer layer（ETL）Upper vacuum evaporation LiF is used as electron injecting layer, thickness 0.5nm.Steamed on LiF layers The Al layers of negative electrode as device is plated, thickness is 150nm.
Device performance see the table below（Device architecture：ITO/2-TNATA(20nm)/NPB（40nm）/ phosphorescence host:15%Ir （ppy）3(30nm)/Bphen（20nm）/LiF（0.5nm）/Al（150nm））
Compound number It is required that brightness cd/m2 Voltage V Current efficiency cd/A
CBP 5000.00 5.9 36.2
1 5000.00 5.3 39.2
4 5000.00 5.4 38.9
5 5000.00 5.4 39.3
7 5000.00 5.5 39.0
8 5000.00 5.4 39.1
10 5000.00 5.4 39.2
13 5000.00 5.4 39.4
Result above shows that new organic materials of the invention are used for organic electroluminescence device, can effectively reduce Landing voltage, improves current efficiency, is phosphorescent light body material of good performance.
Although the present invention is described in conjunction with the embodiments, the invention is not limited in above-described embodiment, it should manage Solution, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and appended claims are summarised The scope of the present invention.

Claims (7)

1. a kind of derivative of carbazolyl-containing, it is characterised in that with the structure as shown in formula (1) or (3)：
Wherein：
One of A and B are N, and another H in CH groups or CH groups is by methyl ,-CF3、-SCH3, phenyl, tolyl, second A kind of substituted group in phenyl, xenyl, carbazyl, N- phenyl carbazole bases；
Ar is selected from singly-bound；Or, when Ar is not singly-bound, Ar structure is selected from following any structures：
R1And R2Separately it is selected from H, methyl, phenyl, tolyl, ethylbenzene, xenyl, carbazyl, carbazyl phenyl, benzene Carbazyl, methyl mercapto or the trifluoromethyl of base substitution；
R3Selected from H, methyl, phenyl, tolyl, ethylbenzene or xenyl；
R4Selected from methyl, phenyl, tolyl, ethylbenzene or xenyl；
N is 1 or 2.
2. the derivative of carbazolyl-containing according to claim 1, it is characterised in that R1And R2Selected from following any structures：
3. the derivative of carbazolyl-containing according to claim 1, it is characterised in that described organic compound is selected from following Structural formula：
4. a kind of application of the derivative of the carbazolyl-containing described in any one of claim 1-3 in organic electroluminescence device.
5. application according to claim 4, it is characterised in that the derivative of described carbazolyl-containing is used as phosphorescence host material Material.
6. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, organic light emission on the substrate Functional layer and cathode layer；Described organic luminescence function layer includes hole transmission layer, organic luminous layer and electron transfer layer, its It is characterised by：
The material of main part of the organic luminous layer is one or more such as the carbazolyl-containing any one of claim 1-3 Derivative.
7. a kind of organic electroluminescence device according to claim 6, it is characterised in that the organic luminous layer is by main body Material and luminescent dye composition, the luminescent dye is phosphorescent coloring.
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