CN104672228B - Fluorene type compound containing carbazole-9-yl group and application thereof - Google Patents
Fluorene type compound containing carbazole-9-yl group and application thereof Download PDFInfo
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- CN104672228B CN104672228B CN201310729422.8A CN201310729422A CN104672228B CN 104672228 B CN104672228 B CN 104672228B CN 201310729422 A CN201310729422 A CN 201310729422A CN 104672228 B CN104672228 B CN 104672228B
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Abstract
The invention provides a fluorene type compound containing a carbazole-9-yl group. The fluorene type compound comprises the structure as shown in formula (1), wherein Ar is selected from fluorenylidene or indenylidenofluorenyl; R1 and R2 are respectively and independently selected from one of H, substituted or unsubstituted C1-12 aliphatic alkyl, C1-12 aliphatic cycloalkyl, aryl with 6-30 carbon atoms and heterocyclic aryl with 6-30 carbon atoms; R3 and R4 are respectively and independently selected from H, C1-12 aliphatic alkyl, C1-12 aliphatic cycloalkyl or C6-30 aryl; L1 and L2 are respectively and independently selected from one of a single bond, C1-20 alkylene, C6-30 substituted or unsubstituted arylene and C6-30 substituted or unsubstituted heteroarylene; and the premise is that R1 and R2 are not H at the same time. The compound has stable nature, the preparation process is simple, and when the compound is used as a phosphorescent host material in an electroluminescent device, the device shows relatively high luminous efficiency and relatively low turn-on voltage. The formula is as described in the specification.
Description
Technical field
A kind of the present invention relates to novel organic compound, and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent material and device, 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, have been achieved for considerable progress.With research
Work deeply and practical during requirement to material, 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 is required with the higher display product of brightness, with phosphor material is
Primary selection.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 the 90% of common steaming component
Left and right, another kind of is phosphorescent coloring, accounts for the 10% about of common steaming component.What tradition used is 4 in phosphorescent light body material, 4 '-N,
N '-two carbazole biphenyl.This material has higher triplet, can be well matched with phosphorescent coloring, but because this material divides
Son amount is less（Molecular weight 484）So that vitrification point is relatively low（Tg about 1100C or once）, easily crystallized using process, shape
Become 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, its
In have research patent pyridine radicals being introduced in material structure（Application number 200680047266.5, publication number
CN101331626A）, also have research patent pyrimidine radicals being introduced in material structure（Application number 200580014777.2, open
Number CN1951155A）, all obtain preferable improvement effect in various degree.
Therefore, based on existing research, develop the phosphorescent light body material of stability and high efficiency further, thus having reduced bright electricity
Pressure, improves device efficiency, has critically important actual application value.
Content of the invention
The purpose of the present invention is to propose to a kind of compound of fluorene class of the base group of -9- containing carbazole, such compound can be used for
ORGANIC ELECTROLUMINESCENCE DISPLAYS field, is used as phosphorescent light body material in 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, the half-life is longer.
For solving above-mentioned technical problem, the technical solution adopted in the present invention is as follows：
Phosphorescent light body material containing imidazo ［ 1,2, a ］ pyridine groups and carbazole group proposed by the present invention, has relatively
High molecular weight, is conducive to the raising of vitrification point, and meanwhile, imidazo [1,2, a] pyridine groups and carbazole group pass through Asia
The fused ring aryl groups such as fluorenyl, sub- indenes fluorenyl are connected, and each substituent group on this 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 no
Sizing film, particularly on the basis of with the presence of carbazyl, present invention introduces imidazo ［ 1,2, a ］ pyridine groups, adjusts effectively
Save the triplet of material（T1）.When the material of the present invention is used for electroluminescent device as phosphorescence host,
Electroluminescent improves significantly opening the everyways such as bright voltage, brightness, service life.
For this reason, the invention provides one kind has as formula（1）The fluorenes class chemical combination of the base group of -9- containing carbazole of shown structure
Thing：
Wherein：
Ar is selected from fluorenylidene or sub- indeno fluorenyl；
R1And R2Separately it is selected from H, carbon number is the substituted or unsubstituted aliphatic alkyl of 1-12, carbon atom
Number is the substituted or unsubstituted aliphatic cycloalkyl of 1-12, carbon number is the substituted or unsubstituted aryl of 6-30, carbon is former
Subnumber is one of substituted or unsubstituted heterocyclic aryl of 6-30；
R3And R4It is respectively and independently selected from H, carbon number is the substituted or unsubstituted aliphatic alkyl of 1-12, carbon number
Substituted or unsubstituted aliphatic cycloalkyl for 1-12 or carbon number are the substituted or unsubstituted aryl of 6-30；
L1And L2Be respectively and independently selected from singly-bound, carbon number be the alkylidene of 1-20, carbon number be 6-30 replacement or not
The arlydene replacing, carbon number are one of substituted or unsubstituted heteroarylidene of 6-30；
Premise is R1And R2It is asynchronously H.
Further, formula（4）Shown structure can directly connect with imidazo ［ 1,2, a ］ pyridine groups, or, work as R1Or
R2During for H, formula（4）Shown structure passes through R1Or R2It is connected with imidazo ［ 1,2, a ］ pyridine groups, be also formula of just succeeding in reaching an agreement（4）Institute
Show that structure is connected directly between R1Or R2Position on；
Further, described R1And R2Separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, just oneself
One of base, phenyl, tolyl, ethylbenzene, xenyl, naphthyl, naphthylphenyl.
When Ar is not singly-bound, formula（1）The framing structure of middle Ar is selected from following structures：
Further, described R3And R4Separately be selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, just oneself
One of base, phenyl, tolyl, ethylbenzene, xenyl.
Further, described bridge linkage group L1And L2It is independently selected from singly-bound, phenylene, biphenylene, naphthylene, sub- pyridine
One of base.
Further, work as R1Or R2When being not H, described 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 of the base group of -9- containing carbazole that can be applicable in organic electroluminescence device
Thing.
Further, the compound of fluorene class of the described -9- containing carbazole base 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 described organic luminous layer is the fluorenes of the base group of -9- containing carbazole described in one or more
Class compound.
Further, in organic electroluminescence device, described luminescent layer is made up of material of main part and luminescent dye, described
Luminescent dye is phosphorescent coloring.
The compound of fluorene class of the base group of -9- containing carbazole that the present invention develops, preparation process is simple, easy and this material tool
There is good heat stability, have the molecular orbit matching with phosphorescent coloring and triplet（T1）,
It organic electroluminescence device is good phosphorescent light body material.
Brief description
In order that present disclosure is more easily understood, specific embodiment below according to the present invention simultaneously combines accompanying drawing,
The present invention is further detailed explanation；Try to achieve the highest occupied molecular of compound with Gaussian03/6-31 method respectively
Track（HOMO）, lowest unoccupied molecular orbital（LUMO）And triplet（T1）.Wherein：
Fig. 1 is the highest occupied molecular orbital(HOMO) of organic compound 1 of the present invention, and HOMO energy level is -5.287ev, three
Line state energy level T1=2.6007ev；
Fig. 2 is the lowest unoccupied molecular orbital of organic compound 1 of the present invention, and lumo energy is -1.456ev；
Specific embodiment
In the present invention, pyridine derivate used, phenyl-bromide are for aldehyde ketone, aryl boric acid derivant, carbazyl boronic acid derivatives
All can chemical products be commercially available at home Deng basic chemical industry raw material, various condensed-nuclei aromatics bromo-derivatives, condensed-nuclei aromatics boric acid derive
Thing all can use common organic procedures synthesis.
Embodiment 1
The synthesis of compound 1
The first step,
2- amino -5- bromopyridine 0.892g is added in the flask of a 50ml（5mmol）, the 2- bromo- 2- phenyl benzene of 1.7g
Ethyl ketone（6mmol）, sodium bicarbonate 0.491g（6mmol）, isopropanol 15ml, return stirring 12hrs, isopropanol is evaporated off, adds
30ml isopropanol and 60ml dichloromethane, collect organic faciess, use pillar layer separation product, petroleum ether and ethyl acetate drip washing, and 3：1
Proportioning.Obtain 1.17g, 67% yield, mp=198-1990C.
Second step,
In one 500 milliliters of there-necked flasks, join magnetic agitation, Ar gas shielded, add 2, the 3- diphenyl -6- bromine imidazoles of 14.9g
And ［ 1,2, a ］ pyridine（Molecular weight 348,0.0428mol）With the THF of 120ml, it is cooled to -78 DEG C, the nBuLi of Deca 25ml2M
（0.05mol）, temperature maintains -78 DEG C always, after stirring 10min when -78 DEG C Deca 30ml B (OiPr)3
（0.153mol）, stir to room temperature and add dilute acid hydrolysis, upper strata is white solid.Filter, separate solid product, water layer is neutralized to
Neutrality, is extracted with ethyl acetate, and extracting solution is evaporated, and adds diluted alkaline, withdraws not molten impurity in alkali with ethyl acetate, and water layer neutralizes
To neutral, there is white solid to separate out, filter, obtain product.There are 11.7g solid product, molecular weight 314, yield 86.46%.
3rd step,
In one 500 milliliters of there-necked flasks, join electric stirring, Ar gas shielded, add the carbazole of 16.7g（Molecular weight 167,
0.10mol）, the bromo- 7- of 2- iodo- 9,9- dimethyl fluorene 44g（Molecular weight 398,0.11mol）, Hydro-Giene (Water Science). 1.9g（Molecular weight 190,
0.01mol）, potassium carbonate 28g（Molecular weight 138,0.203mol）, 18- crown- 6 uses 1.2g（Molecular weight 264,0.00455mol）, plus
Enter the common 250ml of solvent DMPU.Return stirring 4 hours, monitors reaction with TLC.After reaction completely, naturally stir be cooled to 800C with
Under, that is, add 500ml water, stirring, have faint yellow solid product to separate out, leach, 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, join magnetic agitation, add 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- boric acid 9.42g
（Molecular weight 314,0.03mol）, 7-（Carbazole -9- base）- 2- bromo- 9,9- dimethyl fluorene 12.3g（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 displacement, backflow, monitor reaction with TLC, react completely after 4 hours, cooling, separate organic layer, be evaporated, use 1/
10 ethyl acetate/petroleum ether carries out post separation, obtains the compound 1 of 14.31g, molecular weight 627, purity 98.5%, yield
74.5%.
Product MS（m/e）：627, elementary analysiss（C46H33N3）：Theoretical value C：88.01%, H：5.30%, N：6.69%；Real
Measured value C：88.03%, H：5.29%, N：6.68%.
Embodiment 2
The synthesis of compound 2
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 3- phenyl carbazole in the third step
Replace carbazole to make raw material, obtain corresponding monobromo intermediate；Replace 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step
Bromo- 7-（Carbazole -9 base）- 9,9- dimethyl fluorene makees raw material, and other raw materials and process are constant, obtains compound 2.
Product MS（m/e）：703, elementary analysiss（C52H37N3）：Theoretical value C：88.73%, H：5.30%, N：5.97%；Real
Measured value C：88.70%, H：5.28%, N：6.02%.
Embodiment 3
The synthesis of compound 3
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- amino -4- in the first step
Bromopyridine replaces 2- amino -5- bromopyridine to make raw material, obtains a bromo-derivative；Will here with the second step process of synthetic example 1
One bromo-derivative of first step synthesis is made boronic acid derivatives；4th step is replaced with the boronic acid derivatives of the synthesis of second step here
2,3- diphenyl-imidazoles simultaneously ［ 1,2, a ］ pyridine -6- boric acid, other raw materials and process are constant, obtain compound 3.
Product MS（m/e）：627, elementary analysiss（C46H33N3）：Theoretical value C：88.01%, H：5.30%, N：6.69%；Real
Measured value C：88.05%, H：5.32%, N：6.63%.
Embodiment 4
The synthesis of compound 4
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- amino -4- in the first step
Bromopyridine replaces 2- amino -5- bromopyridine to make raw material, obtains a bromo-derivative；Will here first with the second step process of embodiment 1
One bromo-derivative of step synthesis is made boronic acid derivatives；Replace carbazole to make raw material with 3- phenyl carbazole in the third step, obtain corresponding
Monobromo intermediate；Replace the bromo- 7- of 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step（Carbazole -9 base）- 9,9- diformazan
Base fluorenes makees raw material, replaces 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- boron with the boronic acid derivatives of the synthesis of second step here
Acid, other raw materials and process are constant, obtain compound 4.
Product MS（m/e）：703, elementary analysiss（C52H37N3）：Theoretical value C：88.73%, H：5.30%, N：5.97%；Real
Measured value C：88.75%, H：5.32%, N：5.93%.
Embodiment 5
The synthesis of compound 5
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- bromo- 2- benzene in the first step
Base -1-（P-bromophenyl）Ethyl ketone replaces 2- bromo- 2- phenyl acetophenone, replaces 2- amino -5- bromopyridine to make with PA former
Material, obtains a bromo-derivative；With the second step process of synthetic example 1, the bromo-derivative that the first step here synthesizes is made boric acid to spread out
Biological；Replace 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- with the boronic acid derivatives of the synthesis of second step here in the 4th step
Boric acid, other raw materials and process are constant, obtain compound 5.
Product MS（m/e）：627, elementary analysiss（C46H33N3）：Theoretical value C：88.01%, H：5.30%, N：6.69%；Real
Measured value C：88.04%, H：5.34%, N：6.62%.
Embodiment 6
The synthesis of compound 6
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- bromo- 2- benzene in the first step
Base -1-（P-bromophenyl）Ethyl ketone replaces 2- bromo- 2- phenyl acetophenone, replaces 2- amino -5- bromopyridine to make with PA former
Material, obtains a bromo-derivative；With the second step process of synthetic example 1, the bromo-derivative that the first step here synthesizes is made boric acid to spread out
Biological；Replace carbazole to make raw material with 3- phenyl carbazole in the third step, obtain corresponding monobromo intermediate；Is used in the 4th step
The monobromo intermediate of three step synthesis replaces the bromo- 7- of 2-（Carbazole -9 base）- 9,9- dimethyl fluorene makees raw material, with the synthesis of second step here
Boronic acid derivatives replace 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- boric acid, other raw materials and process constant, changed
Compound 6.
Product MS（m/e）：703, elementary analysiss（C52H37N3）：Theoretical value C：88.73%, H：5.30%, N：5.97%；Real
Measured value C：88.71%, H：5.34%, N：5.95%.
Embodiment 7
The synthesis of compound 7
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use the bromo- 2- of 2- in the first step（Right
Bromophenyl）1-Phenylethanone. replaces 2- bromo- 2- phenyl acetophenone, replaces with PA 2- amino -5- bromopyridine to make raw material, obtains
One bromo-derivative；With the second step process of synthetic example 1, the bromo-derivative that the first step here synthesizes is made boronic acid derivatives；?
2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- boric acid is replaced with the boronic acid derivatives of the synthesis of second step here in 4th step, its
Its raw material and process are constant, obtain compound 7.
Product MS（m/e）：627, elementary analysiss（C46H33N3）：Theoretical value C：88.01%, H：5.30%, N：6.69%；Real
Measured value C：88.02%, H：5.34%, N：6.64%.
Embodiment 8
The synthesis of compound 8
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use the bromo- 2- of 2- in the first step（Right
Bromophenyl）1-Phenylethanone. replaces 2- bromo- 2- phenyl acetophenone, replaces with PA 2- amino -5- bromopyridine to make raw material, obtains
One bromo-derivative；With the second step process of synthetic example 1, the bromo-derivative that the first step here synthesizes is made boronic acid derivatives；?
Replace carbazole to make raw material with 3- phenyl carbazole in 3rd step, obtain corresponding monobromo intermediate；4th step is closed with the 3rd step
The monobromo intermediate becoming replaces the bromo- 7- of 2-（Carbazole -9 base）- 9,9- dimethyl fluorene makees raw material, with the boric acid of the synthesis of second step here
Derivant replaces 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine -6- boric acid, other raw materials and process constant, obtains compound 8.
Product MS（m/e）：703, elementary analysiss（C52H37N3）：Theoretical value C：88.73%, H：5.30%, N：5.97%；Real
Measured value C：88.74%, H：5.34%, N：5.92%.
Embodiment 9
The synthesis of compound 9
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- bromo- 7- iodine in the third step
Indeno ［ 3,2, b ］ fluorenes replaces 2- bromo- 7- iodine fluorenes to make raw material, replaces 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step
Iodo- 9, the 9- dimethyl fluorene of bromo- 7-, other raw materials and process are constant, obtain compound 9.
Product MS（m/e）：743, elementary analysiss（C55H41N3）：Theoretical value C：88.80%, H：5.55%, N：5.65%；Real
Measured value C：88.82%, H：5.51%, N：5.67%.
Embodiment 10
The synthesis of compound 10
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 3- phenyl carbazole in the third step
Replace carbazole, replace iodo- 9, the 9- dimethyl fluorene of the bromo- 7- of 2- to make raw material with the bromo- 7- of 2- iodo- tetramethyl indeno ［ 3,2, b ］ fluorenes, obtain
Corresponding monobromo intermediate；Replace the bromo- 7- of 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step（Carbazole -9 base）-9,9-
Dimethyl fluorene makees raw material, and other raw materials and process are constant, obtains compound 10.
Product MS（m/e）：819, elementary analysiss（C61H45N3）：Theoretical value C：89.34%, H：5.53%, N：5.12%；Real
Measured value C：89.36%, H：5.55%, N：5.09%.
Embodiment 11
The synthesis of compound 11
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- amino -4- in the first step
Bromopyridine replaces 2- amino -5- bromopyridine to make raw material, obtains a bromo-derivative；Will here with the second step process of synthetic example 1
One bromo-derivative of first step synthesis is made boronic acid derivatives；Use the bromo- 7- of 2- iodo- tetramethyl indeno ［ 3,2, b ］ fluorenes in the third step
Replace iodo- 9, the 9- dimethyl fluorene of the bromo- 7- of 2- to make raw material, obtain corresponding monobromo intermediate；4th step is synthesized with the 3rd step
Monobromo intermediate replace the bromo- 7- of 2-（Carbazole -9 base）- 9,9- dimethyl fluorene makees raw material, and other raw materials and process are constant, obtain
Compound 11.
Product MS（m/e）：743, elementary analysiss（C55H41N3）：Theoretical value C：88.80%, H：5.55%, N：5.65%；Real
Measured value C：88.83%, H：5.50%, N：5.67%.
Embodiment 12
The synthesis of compound 12
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use 2- amino -4- in the first step
Bromopyridine replaces 2- amino -5- bromopyridine to make raw material, obtains a bromo-derivative；Will here with the second step process of synthetic example 1
One bromo-derivative of first step synthesis is made boronic acid derivatives；Replace carbazole with 3- phenyl carbazole in the third step, with the bromo- 7- of 2-
Iodo- tetramethyl indeno ［ 3,2, b ］ fluorenes replaces iodo- 9, the 9- dimethyl fluorene of the bromo- 7- of 2- to make raw material, obtains corresponding monobromo intermediate；
Replace the bromo- 7- of 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step（Carbazole -9 base）- 9,9- dimethyl fluorene, with here the
The boronic acid derivatives of two steps synthesis replace 2,3- diphenyl-imidazole, and simultaneously ［ 1,2, a ］ pyridine -6- boric acid makees raw material, other raw materials and mistake
Journey is constant, obtains compound 12.
Product MS（m/e）：819, elementary analysiss（C61H45N3）：Theoretical value C：89.34%, H：5.53%, N：5.12%；Real
Measured value C：89.35%, H：5.57%, N：5.08%.
Embodiment 13
The synthesis of compound 13
Building-up process is allocated as four steps, is same as the four-step reaction of embodiment 1 respectively.Simply use PA in the first step
Replace 2- amino -5- bromopyridine, with 2- bromo- 2- phenyl -1-（P-bromophenyl）It is former that ethyl ketone replaces 2- bromo- 2- phenyl acetophenone to make
Material, obtains a bromo-derivative；With the second step process of synthetic example 1, the bromo-derivative that the first step here synthesizes is made boric acid to spread out
Biological；The bromo- 7- of 2- iodo- tetramethyl indeno ［ 3,2, b ］ fluorenes is used to replace iodo- 9, the 9- dimethyl fluorene of the bromo- 7- of 2- to make in the third step former
Material, obtains corresponding monobromo intermediate；Replace the bromo- 7- of 2- with the monobromo intermediate of the 3rd step synthesis in the 4th step（Carbazole -9
Base）- 9,9- dimethyl fluorene, with second step here synthesis boronic acid derivatives replace 2,3- diphenyl-imidazole simultaneously ［ 1,2, a ］ pyridine-
6- boric acid makees raw material, and other raw materials and process are constant, obtains compound 13.
Product MS（m/e）：743, elementary analysiss（C55H41N3）：Theoretical value C：88.80%, H：5.55%, N：5.65%；Real
Measured value C：88.82%, H：5.56%, N：5.62%.
Embodiment 14
The synthesis of compound 14
Building-up process is same as the four-step reaction of embodiment 1, simply uses the bromo- 7- of 2-（9- carbazyl）- tetramethyl indeno 3,
2, b ］ fluorenes replaces the bromo- 7- of 2-（Carbazole -9 base）- 9,9- dimethyl fluorene, uses 4-（2- phenylimidazole simultaneously ［ 1,2, a ］ pyridin-3-yl）Benzene
Boric acid replaces 2,3- diphenyl-imidazole, and simultaneously ［ 1,2, a ］ pyridine -6- boric acid makees raw material, and other raw materials and process are constant, obtain chemical combination
Thing 14.
Product MS（m/e）：743, elementary analysiss（C55H41N3）：Theoretical value C：88.80%, H：5.55%, N：5.65%；Real
Measured value C：88.81%, H：5.59%, N：5.60%.
The Application Example of the compounds of this invention is presented herein below：
Embodiment 15：The preparation of electroluminescent device and result
Prepare the preferred implementation of device：
（1）Device designs
Compare the performance of these materials for convenience, 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 using compound 1,2,
4th, 5,7,10,13 as phosphorescent light body material illustration, CBP or NPB or mCP compares material, Ir as phosphorescence host（ppy）3、Ir
(piq)3With Firpic respectively as phosphorescent coloring.The structure of CBP and phosphorescent coloring is：
Substrate can be using the substrate in conventional organic luminescence device, such as：Glass or plastics.Device system in the present invention
Glass substrate is selected, ITO makees anode material in work.
Hole transmission layer can adopt various tri-arylamine group materials.Selected hole in the element manufacturing of the present invention passes
Defeated material is NPB.
In the element manufacturing of the present invention, selected electron transport material is Bphen.
Negative electrode can adopt 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.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 supersound process in commercial detergent will be coated with, rinses in deionized water,
In acetone：Ultrasonic oil removing in alcohol mixed solvent, is baked under clean environment and completely removes moisture content, clear with ultraviolet light and ozone
Wash, and with mental retardation cation bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum intracavity, is evacuated to 1 × 10-5～9 × 10-3Pa, above-mentioned
On anode tunic, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 40nm；
On hole transmission layer, the phosphorescent light body material 1,2,4,5,7,10,13 of the vacuum evaporation present invention, steams simultaneously altogether
Plating phosphorescent coloring Ir（ppy）3（Or FIrpic, or Ir（piq）3）, phosphorescent light body material also can be with CBP or NPB or mCP generation
Replace.Phosphorescence host and dyestuff are deposited with the luminescent layer as device altogether, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm,
Photoinitiator dye Ir（ppy）3 doping content is the doping content of 10%, FIrpic is 12%, Ir（piq）3Doping content be 5%, this
In described doping content refer to that the evaporation rate ratio of luminescent dye and material of main part is 10:100,12:100,5:100；
On luminescent layer, as the electron transfer layer of device, its evaporation rate is vacuum evaporation one stratification compound Bphen
0.1nm/s, evaporation total film thickness is 20nm；
In electron transfer layer（ETL）Upper vacuum evaporation LiF is as electron injecting layer, thickness 0.5nm.Steam on LiF layer
As the negative electrode of device, thickness is 150nm to plating Al layer.
Device performance see table（Device architecture：ITO/NPB（40nm）/ phosphorescence host:Phosphorescent coloring (30nm)/Bphen
（20nm）/LiF（0.5nm）/Al（150nm））
Result above shows, the new organic materials of the present invention are used for organic electroluminescence device, can effectively reduce
Landing voltage, improves current efficiency, is material of main part of good performance.
Although describe the present invention 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 claims summarise
The scope of the present invention.
Claims (10)
1. a kind of compound of fluorene class of the base group of -9- containing carbazole is it is characterised in that have the structure as shown in formula (1)：
Wherein：
Ar is selected from fluorenylidene or sub- indeno fluorenyl；
R1And R2Separately it is selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene
One of base, xenyl, naphthyl, naphthylphenyl；
R3And R4It is respectively and independently selected from H, the carbon number aliphatic alkyl for 1-12, carbon number is the aliphatic cycloalkanes of 1-12
Base or carbon number are the aryl of 6-30；
L1And L2It is respectively and independently selected from one of singly-bound, phenylene, biphenylene, naphthylene, pyridylidene；
Premise is R1And R2It is asynchronously H.
2. the compound of fluorene class of the base group of -9- containing carbazole according to claim 1 is it is characterised in that when Ar is not singly-bound
When, the structure of Ar is selected from following structures：
3. the compound of fluorene class of the base group of -9- containing carbazole according to claim 1 is it is characterised in that described R3And R4Respectively
Independently selected from H, methyl, ethyl, propyl group, normal-butyl, n-pentyl, n-hexyl, phenyl, tolyl, ethylbenzene, xenyl wherein
One of.
4. the compound of fluorene class of the base group of -9- containing carbazole according to claim 1 is it is characterised in that work as R1Or R2It is not H
When, described R1Or R2Selected from following structures：
5. the compound of fluorene class of the base group of -9- containing carbazole according to claim 1 is it is characterised in that described organises
Compound is selected from following structural formula：
6. a kind of compound of fluorene class of the base group of -9- containing carbazole is it is characterised in that described organic compound is selected from following structure
Formula：
7. a kind of compound of fluorene class of the base group of -9- containing carbazole described in any one of claim 1-6 is sent out preparing organic electroluminescence
Application in optical device.
8. application according to claim 7 is it is characterised in that the compound of fluorene class of the described base group of -9- containing carbazole is used
Make phosphorescent light body material.
9. a kind of organic electroluminescence device, including substrate, and sequentially forms anode layer on the substrate, organic light emission
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 described organic luminous layer is one or more -9- containing carbazole as any one of claim 1-6
The compound of fluorene class of base group.
10. a kind of organic electroluminescence device according to claim 9 is it is characterised in that described organic luminous layer is by leading
Body material and luminescent dye composition, described luminescent dye is phosphorescent coloring.
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| WO2012108879A1 (en) * | 2011-02-11 | 2012-08-16 | Universal Display Corporation | Organic light emitting device and materials for use in same |
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