CN104672229B - A kind of fluorene kind derivative of base group containing carbazole 3 and its application - Google Patents
A kind of fluorene kind derivative of base group containing carbazole 3 and its application Download PDFInfo
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Abstract
The invention provides a kind of compound of fluorene class of the base group containing carbazole 3, with such as formula（1）Shown structure：Wherein：Ar is selected from fluorenylidene or sub- indeno fluorenyl；R1And R2Independently selected from one of H, substituted or unsubstituted C1 12 aliphatic alkyl, C1 12 aliphatic cycloalkyl, C6 30 aryl, C6 30 heterocyclic aryl；R3Aliphatic alkyl selected from C1 12, C1 12 aliphatic cycloalkyl or carbon number are 6 30 aryl；R4The aryl of aliphatic alkyl selected from H, C1 12, C1 12 aliphatic cycloalkyl or C6 30；L1And L2It is independently selected from singly-bound, C1 20 alkylidene, C6 30 substituted or unsubstituted arlydene or heteroarylidene；On condition that R1And R2It is asynchronously H.Such compound property is stable, and preparation technology is simple, when being used as phosphorescent light body material in electroluminescent device, and device shows higher luminous efficiency and relatively low opens bright voltage.
Description
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 measures smaller (molecular weight 484) so that glass transition temperature is relatively low (Tg about 1100C or once), is easily being 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 research patent (application number 200680047266.5, publication number that pyridine radicals is introduced into material structure
CN101331626A), also there are research patent (application number 200580014777.2, disclosure that pyrimidine radicals is introduced into material structure
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 compound of fluorene class of the bases of -3- containing carbazole group, such compound can be used for
It is used as phosphorescent light body material in ORGANIC ELECTROLUMINESCENCE DISPLAYS field, the organic luminescence function layer in organic electroluminescent device, enters
And obtain that driving voltage is low, the organic electroluminescence device that current efficiency is high, half-life period is longer.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
The phosphorescent light body material containing imidazo [1,2, a] pyridine groups and carbazole group that the present invention is provided, with compared with
High molecular weight, is conducive to the raising of glass transition temperature, meanwhile, imidazo [1,2, a] pyridine groups and carbazole group pass through Asia
The fused ring aryl groups such as fluorenyl, sub- indenes And fluorenyls are connected, and each substituent in the compound is in on-plane surface state so that whole
Individual molecule forms distortion to a certain extent on space multistory, and the stereoeffect of molecule is irregular, advantageously forms nothing
Sizing film, particularly on the basis of with the presence of carbazyl, present invention introduces imidazo [1,2, a] pyridine groups, is effectively adjusted
The triplet (T1) of material is saved.When the material of the present invention is used for into electroluminescent device as phosphorescence host,
Electroluminescent improves significantly opening the everyways such as bright voltage, brightness, service life.
Therefore, the invention provides a kind of fluorenes class chemical combination of the base groups of -3- containing carbazole of the structure with as shown in formula (1)
Thing：
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 one of 6-30 substituted or unsubstituted heterocyclic aryl；
R3Substitution that substituted or unsubstituted aliphatic alkyl, the carbon number for being 1-12 selected from carbon number are 1-12 or
Unsubstituted aliphatic cycloalkyl or the substituted or unsubstituted aryl that carbon number is 6-30；
R4The substitution that substituted or unsubstituted aliphatic alkyl, the carbon number for being 1-12 selected from H, carbon number are 1-12
Or the substituted or unsubstituted aryl that unsubstituted aliphatic cycloalkyl or carbon number are 6-30；
L1And L2It is respectively and independently selected from substitution that alkylidene, carbon number that singly-bound, carbon number are 1-20 are 6-30 or not
Substituted arlydene or the substituted or unsubstituted heteroarylidene that carbon number is 6-30；On condition that R1And R2It is asynchronously H.
Further, structure shown in formula (4) can be connected directly with imidazo [1,2, a] pyridine groups, or, work as R1Or
R2During for H, structure shown in formula (4) passes through R1Or R2It is connected with imidazo [1,2, a] pyridine groups, is also just to succeed in reaching an agreement formula (4) institute
Show that structure is connected directly between R1Or R2Position on；
Further, the R1And R2Separately selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, just oneself
One of base, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, naphthylphenyl.
In formula (1), Ar skeleton structure is selected from following structures：
Further, the R3Selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, second
One of phenyl, xenyl.
Further, the R4Selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl,
One of ethylbenzene, xenyl.
Further, the bridge linkage group L1And L2It is independently selected from singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine
One of base.
Further, R is worked as1Or R2When being not H, the R1Or R2Selected from following 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 fluorenes class chemical combination for the base groups of -3- containing carbazole that can be applied in organic electroluminescence device
Thing.
Further, the compound of fluorene class of the bases of -3- containing the carbazole group can be used as in organic electroluminescence device
Phosphorescent light body 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 fluorenes of the base groups of -3- containing carbazole described in one or more
Class compound.
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 compound of fluorene class for the base groups of -3- containing carbazole that the present invention is developed, preparation technology is simple, easy and the material has
There is good heat endurance, have the molecular orbit matched with phosphorescent coloring and triplet (T1), in organic electroluminescent
It is good phosphorescent light body material in device.
Specific embodiment：
Example 1 below-embodiment 19 is the synthetic example of the application：
Pyridine derivate used, phenyl-bromide are for aldehyde ketone, aryl boric acid derivative, carbazyl boronic acid derivatives in the present invention
Chemical products it can be commercially available at home Deng basic chemical industry raw material, various condensed-nuclei aromatics bromo-derivatives, condensed-nuclei aromatics boric acid derive
Thing can use common organic procedures to synthesize.
Embodiment 1
The synthesis of following structural compounds,
The first step,
2- amino -5- bromopyridines 0.892g (5mmol), the 1.7g bromo- 2- phenyl benzene of 2- are added in the flask of a 50ml
Ethyl ketone (6mmol), sodium acid carbonate 0.491g (6mmol), isopropanol 15ml, return stirring 12hrs, is evaporated off isopropanol, adds
30ml isopropanols and 60ml dichloromethane, collect organic phase, use pillar layer separation product, petroleum ether and ethyl acetate elution, 3：1
Proportioning.Obtain 1.17g, 67% yield, mp=198-199 DEG C.
Second step,
In one 500 milliliters of there-necked flasks, with magnetic agitation, Ar gas shieldeds add 14.9g 2,3- diphenyl -6- bromine imidazoles
And [1,2, a] pyridine (molecular weight 348,0.0428mol) and 120ml THF, it is cooled to -78 DEG C, 25ml2M nBuLi is added dropwise
(0.05mol), temperature maintains the B (OiPr) that 30ml is added dropwise after -78 DEG C, stirring 10min at -78 DEG C always3
(0.153mol), stirs and dilute acid hydrolysis is added to room temperature, and upper strata is white solid.Filtering, separates solid product, water layer is neutralized to
Neutrality, is extracted with ethyl acetate, and extract solution is evaporated, and adds diluted alkaline, and the not molten impurity in alkali is withdrawn with ethyl acetate, and water layer is neutralized
To neutral, there is white solid precipitation, filter, obtain product.It there are 11.7g solid products, molecular weight 314, yield 86.46%.
3rd step,
In one 500 milliliters of there-necked flasks, with electric stirring, Ar gas shieldeds, add 16.7g carbazole (molecular weight 167,
0.10mol), iodo- 9, the 9- dimethyl fluorenes 44g of the bromo- 7- of 2- (molecular weight 398,0.11mol), cuprous iodide 1.9g (molecular weight 190,
0.01mol), potassium carbonate 28g (molecular weight 138,0.203mol), the 1.2g (molecular weight 264,0.00455mol) of 18- crown-s 6, plus
Enter the common 250ml of solvent DMPU.Return stirring 4 hours, is monitored with TLC and reacted.Reaction completely after, naturally stir be cooled to 800C with
Under, that is, 500ml water is added, stirring has the precipitation of faint yellow solid product, filters out, dry.Separated with silica gel column chromatography, obtain micro-
Yellow product 35.7g, molecular weight 437, purity 98.0%, yield 80.2%.
4th step,
1000 milliliters of there-necked flasks, with magnetic agitation, add 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid 9.42g
(molecular weight 314,0.03mol), 7- bromo- 9, the 9- dimethyl fluorenes 12.3g of (carbazole -9- bases) -2- (molecular weight 437,0.028mol),
Pd(PPh3)4Usage amount 1.8g (molecular weight 1154,0.00155mol), sodium carbonate 175ml (2M), toluene 175ml, ethanol
175ml.After argon gas displacement, backflow is monitored with TLC and reacted, and reacts complete after 4 hours, and cooling separates organic layer, is evaporated, with 1/
10 ethyl acetate/petroleum ether carries out post separation, obtains 14.31g compound, molecular weight 627, purity 98.5%, yield
74.5%.
Product MS (m/e)：627, elementary analysis (C46H33N3)：Theoretical value C：88.01%, H：5.30%, N：6.69%；It is real
Measured value C：88.03%, H：5.29%, N：6.68%.
Embodiment 2
The synthesis of compound 1
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl-imidazoles are replaced simultaneously with N- phenyl carbazole -3- boric acid
[1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step reaction is same
In the step of embodiment 1 the 4th, the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, its
Its raw material and process are constant, obtain compound 1.
Product MS (m/e)：819, elementary analysis (C61H45N3)：Theoretical value C：89.34%, H：5.53%, N：5.12%；It is real
Measured value C：89.33%, H：5.57%, N：5.10%.
Embodiment 3
The synthesis of compound 2
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl-imidazoles are replaced simultaneously with N- phenyl carbazole -3- boric acid
[1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step reaction is same
In the step of embodiment 1 the 4th, the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, uses
Simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid to 2,3- diphenyl-imidazoles, other
Reagent and process are constant, obtain compound 2.
Product MS (m/e)：819, elementary analysis (C61H45N3)：Theoretical value C：89.34%, H：5.53%, N：5.12%；It is real
Measured value C：89.31%, H：5.52%, N：5.17%.
Embodiment 4
The synthesis of compound 3
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl-imidazoles are replaced simultaneously with N- phenyl carbazole -3- boric acid
[1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step reaction is same
In the step of embodiment 1 the 4th, the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, uses
4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid,
Other reagents and process are constant, obtain compound 3.
Product MS (m/e)：819, elementary analysis (C61H45N3)：Theoretical value C：89.34%, H：5.53%, N：5.12%；It is real
Measured value C：89.30%, H：5.53%, N：5.17%.
Embodiment 5
The synthesis of compound 4
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with the iodo- tetramethyl indenos of the bromo- 7- of 2-
[3,2, b] fluorenes replaces iodo- 9, the 9- dimethyl fluorenes of the bromo- 7- of 2-, and 2,3- diphenyl-imidazoles are replaced simultaneously with N- phenyl carbazole -3- boric acid
[1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding monobromo intermediate；Second step reaction is same
In the step of embodiment 1 the 4th, the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, uses
4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid,
Other reagents and process are constant, obtain compound 4.
Product MS (m/e)：819, elementary analysis (C61H45N3)：Theoretical value C：89.34%, H：5.53%, N：5.12%；It is real
Measured value C：89.28%, H：5.55%, N：5.17%.
Embodiment 6
The synthesis of compound 5
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, is replaced with N- phenyl carbazole -3- boric acid
Simultaneously [1,2, a] pyridine -6- boric acid makees raw material to 2,3- diphenyl-imidazoles, and other reagents and process are constant, obtain in corresponding monobromo
Mesosome；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (carbazoles -9 of 3-
Base) -9,9- dimethyl fluorenes, other raw materials and process be constant, obtains compound 5.
Product MS (m/e)：703, elementary analysis (C52H37N3)：Theoretical value C：88.73%, H：5.30%, N：5.97%；It is real
Measured value C：88.76%, H：5.32%, N：5.92%.
Embodiment 7
The synthesis of compound 6
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with N- phenyl -6- phenyl carbazole -3- boron
Acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (clicks of 3-
The base of azoles -9) -9,9- dimethyl fluorenes, other reagents and process be constant, obtains compound 6.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.34%, H：5.32%, N：5.34%.
Embodiment 8
The synthesis of compound 7
Building-up process is allocated as three steps.First step reaction is same as the step of embodiment 1 the 4th, is replaced with N- phenyl carbazole -3- boric acid
Simultaneously [1,2, a] pyridine -6- boric acid makees raw material to 2,3- diphenyl-imidazoles, and other reagents and process are constant, obtain in corresponding monobromo
Mesosome；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (carbazoles -9 of 3-
Base) -9,9- dimethyl fluorenes, p-bromophenyl phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, Qi Tashi
Agent and process are constant, obtain second step reaction product monobromo intermediate；Three-step reaction is same as the step of embodiment 1 the 4th, with second
The monobromo intermediate of step synthesis replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, obtains compound 6.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.35%, H：5.29%, N：5.36%.
Embodiment 9
The synthesis of compound 8
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with 4- (N- phenyl carbazole -3- bases) benzene
Boric acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3-
(base of carbazole -9) -9,9- dimethyl fluorenes, other reagents and process are constant, obtain compound 8.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.34%, H：5.28%, N：5.38%.
Embodiment 10
The synthesis of compound 9
Building-up process is allocated as two steps, and the four-step reaction of embodiment 1 is same as respectively.First step reaction is same as embodiment 1 the 4th
Step, 2,3- diphenyl-imidazoles are replaced with N- phenyl carbazole -3- boric acid, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, other reagents and
Process is constant, obtains corresponding monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, the monobromo synthesized with the first step
Intermediate replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, with 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -7- boric acid
Instead of 2,3- diphenyl-imidazoles, simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other raw materials and process are constant, obtain compound 9.
Product MS (m/e)：703, elementary analysis (C52H37N3)：Theoretical value C：88.73%, H：5.30%, N：5.97%；It is real
Measured value C：88.74%, H：5.34%, N：5.92%.
Embodiment 11
The synthesis of compound 10
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with N- phenyl -6- phenyl carbazole -3- boron
Acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (clicks of 3-
The base of azoles -9) -9,9- dimethyl fluorenes, with 2,3- diphenyl-imidazoles, simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously
[1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 10.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.34%, H：5.28%, N：5.38%.
Embodiment 12
The synthesis of compound 11
Building-up process is allocated as three steps.First step reaction is same as the step of embodiment 1 the 4th, is replaced with N- phenyl carbazole -3- boric acid
Simultaneously [1,2, a] pyridine -6- boric acid makees raw material to 2,3- diphenyl-imidazoles, and other reagents and process are constant, obtain in corresponding monobromo
Mesosome；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (carbazoles -9 of 3-
Base) -9,9- dimethyl fluorenes, p-bromophenyl phenyl boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, Qi Tashi
Agent and process are constant, obtain second step reaction product monobromo intermediate；Three-step reaction is same as the step of embodiment 1 the 4th, with second
Step synthesis monobromo intermediate replace the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, with 2,3- diphenyl-imidazoles simultaneously [1,2,
A] pyridine -7- boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, obtains compound 11.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.30%, H：5.34%, N：5.36%.
Embodiment 13
The synthesis of compound 12
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with 4- (N- phenyl carbazole -3- bases) benzene
Boric acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3-
(base of carbazole -9) -9,9- dimethyl fluorenes, with 2,3- diphenyl-imidazoles, simultaneously [1,2, a] pyridine -7- boric acid replaces 2,3- diphenyl miaows
Azoles simultaneously [1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 12.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.33%, H：5.32%, N：5.35%.
Embodiment 14
The synthesis of compound 13
Building-up process is allocated as two steps, and the four-step reaction of embodiment 1 is same as respectively.First step reaction is same as embodiment 1 the 4th
Step, 2,3- diphenyl-imidazoles are replaced with N- phenyl carbazole -3- boric acid, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, other reagents and
Process is constant, obtains corresponding monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, the monobromo synthesized with the first step
Intermediate replaces the bromo- 7- of 3- (base of carbazole -9) -9,9- dimethyl fluorenes, with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) benzene
Boric acid replaces 2,3- diphenyl-imidazoles simultaneously [1,2, a] pyridine -6- boric acid, and other raw materials and process are constant, obtain compound 13.
Product MS (m/e)：703, elementary analysis (C52H37N3)：Theoretical value C：88.73%, H：5.30%, N：5.97%；It is real
Measured value C：88.71%, H：5.34%, N：5.95%.
Embodiment 15
The synthesis of compound 14
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with N- phenyl -6- phenyl carbazole -3- boron
Acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (clicks of 3-
The base of azoles -9) -9,9- dimethyl fluorenes, replace 2,3- diphenyl miaows with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid
Azoles simultaneously [1,2, a] pyridine -6- boric acid, other raw materials and process are constant, obtain compound 14.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.32%, H：5.34%, N：5.34%.
Embodiment 16
The synthesis of compound 15
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with 4- (N- phenyl carbazole -3- bases) benzene
Boric acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3-
(base of carbazole -9) -9,9- dimethyl fluorenes, 2,3- hexichol is replaced with 4- (3- phenylimidazoles simultaneously [1,2, a] pyridine -2- bases) phenyl boric acid
Base imidazo [1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 15.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.30%, H：5.33%, N：5.37%.
Embodiment 17
The synthesis of compound 16
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, is replaced with N- phenyl carbazole -3- boric acid
Simultaneously [1,2, a] pyridine -6- boric acid makees raw material to 2,3- diphenyl-imidazoles, and other reagents and process are constant, obtain in corresponding monobromo
Mesosome；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (carbazoles -9 of 3-
Base) -9,9- dimethyl fluorenes, replace 2,3- diphenyl-imidazoles simultaneously with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid
[1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 16.
Product MS (m/e)：703, elementary analysis (C52H37N3)：Theoretical value C：88.73%, H：5.30%, N：5.97%；It is real
Measured value C：88.75%, H：5.31%, N：5.94%.
Embodiment 18
The synthesis of compound 17
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with N- phenyl -6- phenyl carbazole -3- boron
Acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- (clicks of 3-
The base of azoles -9) -9,9- dimethyl fluorenes, replace 2,3- diphenyl miaows with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid
Azoles simultaneously [1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 17.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.32%, H：5.32%, N：5.36%.
Embodiment 19
The synthesis of compound 18
Building-up process is allocated as two steps.First step reaction is same as the step of embodiment 1 the 4th, with 4- (N- phenyl carbazole -3- bases) benzene
Boric acid replaces 2,3- diphenyl-imidazoles, and simultaneously [1,2, a] pyridine -6- boric acid makees raw material, and other reagents and process are constant, obtains corresponding
Monobromo intermediate；Second step reaction is same as the step of embodiment 1 the 4th, and the monobromo intermediate synthesized with the first step replaces the bromo- 7- of 3-
(base of carbazole -9) -9,9- dimethyl fluorenes, 2,3- hexichol is replaced with 4- (2- phenylimidazoles simultaneously [1,2, a] pyridin-3-yl) phenyl boric acid
Base imidazo [1,2, a] pyridine -6- boric acid, other reagents and process are constant, obtain compound 18.
Product MS (m/e)：779, elementary analysis (C58H41N3)：Theoretical value C：89.31%, H：5.30%, N：5.39%；It is real
Measured value C：89.34%, H：5.31%, N：5.35%.
Here is the Application Example of the compounds of this invention：
Embodiment 20
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 devise a simple electroluminescent device (substrate/anode/
Hole transmission layer (HTL)/phosphorescent coloring/phosphorescence host (EL)/electron transfer layer (ETL)/negative electrode), using only compound 1,3,
7th, 8,10,12,13,15,17 and 18 as phosphorescent light body material illustration, and CBP or NPB or mCP compare material as phosphorescence host,
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, for example：Glass or plastics.In the device system of the present invention
Glass substrate is selected in work, ITO makees anode material.
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.
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/Al.The selected electron injection in the element manufacturing of the present invention
Material is LiF, and 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 × 10-3Pa, above-mentioned
Vacuum evaporation NPB is as hole transmission layer on anode tunic, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm；
The phosphorescent light body material of the vacuum evaporation present invention is (with 1,3,7,8,10,12,13,15,17 on hole transmission layer
Exemplified by 18), while evaporation phosphorescent coloring Ir (ppy) altogether3(or FIrpic, or Ir (piq)3), phosphorescent light body material also can use
CBP or NPB or mCP is replaced.The luminescent layer as device is deposited in phosphorescence host and dyestuff altogether, and evaporation rate is 0.1nm/s, evaporation
Total film thickness is 30nm, luminescent dye Ir (ppy)3Doping concentration be 10%, FIrpic doping concentration be 12%, Ir (piq)3
Doping concentration be 5%, doping concentration mentioned here refers to that the evaporation rate ratio of luminescent dye and material of main part is 10:
100,12:100,5:100；
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；
Vacuum evaporation LiF is used as electron injecting layer, thickness 0.5nm on electron transfer layer (ETL).Steamed on LiF layers
The Al layers of negative electrode as device is plated, thickness is 150nm.
Device device performance see the table below (device architecture：ITO/NPB (40nm)/phosphorescent coloring/phosphorescence host (30nm)/Bphen
(20nm)/LiF(0.5nm)/Al(150nm))
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 compound of fluorene class of the bases of -3- containing carbazole group, it is characterised in that with the structure as shown in formula (1)：
Wherein：
The R1And R2Separately selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl,
One of ethylbenzene, xenyl, naphthyl, naphthylphenyl；
The R3 be selected from methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl its
One of；
The R4Selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl
One of them；
The bridge linkage group L1And L2It is independently selected from one of singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine radicals；Before
It is R to carry1And R2It is asynchronously H；
The Ar is selected from following structures：
2. the compound of fluorene class of the bases of -3- containing carbazole group according to claim 1, it is characterised in that work as R1Or R2It is not H
When, the R1Or R2Selected from following structures：
3. the compound of fluorene class of the bases of -3- containing carbazole group according to claim 1, it is characterised in that it is described containing carbazole -
The compound of fluorene class of 3- base groups is selected from following structural formula：
4. the compound of fluorene class of the base groups of -3- containing carbazole in claim 1-3 described in any one is in organic electroluminescence
Application in part.
5. application according to claim 4, it is characterised in that the compound of fluorene class of the bases of -3- containing the carbazole group is used as
Phosphorescent light body material in organic electroluminescence device.
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 -3- containing carbazole as any one of claim 1-4
The compound of fluorene class of base group.
7. a kind of organic electroluminescence device according to claim 6, it is characterised in that the luminescent layer is by material of main part
With luminescent dye composition, the luminescent dye is phosphorescent coloring.
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