CN109180665A - The conjugated compound of the thioxanthene of diphenyl containing 9,9- and preparation and application - Google Patents
The conjugated compound of the thioxanthene of diphenyl containing 9,9- and preparation and application Download PDFInfo
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Abstract
The invention belongs to electroluminescent material technical fields, disclose conjugated compound and the preparation and application of one kind thioxanthene Han 9,9- diphenyl.The conjugated compound for containing 9,9- diphenyl thioxanthene has general structure shown in formula 1 or formula 2, wherein R1And R2The conjugate unit or alkyl and the simultaneously-substituted conjugate unit of alkoxy that aromatic heterocycle, the aromatic heterocycle of carbon silicon hydrogen atom composition, the alkyl of C1~C24, alkyl-substituted conjugate unit, the alkoxy that aromatic heterocycle, the carbon sulphur hydrogen atom of aromatic heterocycle, carbon nitrogen oxygen hydrogen atom composition that aromatic rings, the carbon nitrogen hydrogen atom constituted for the identical or different ethylene support group with electron, acetylene support group, hydrocarbon atom is constituted are constituted replace.Gained compound of the invention has fluorescence, and the external quantum efficiency of device can be obviously improved as the luminescent layer of organic electroluminescent LED.
Description
Technical field
The invention belongs to electroluminescent material technical fields, and in particular to a kind of conjugation chemical combination of the thioxanthene Han 9,9- diphenyl
Object and preparation and application.
Background technique
Organic electroluminescent LED (OLED) because have efficiently, low voltage drive, be easy to large area preparation and panchromatic aobvious
The advantages that showing has broad application prospects, and obtains the extensive concern of people.The research starts from the last century 50's, until
Doctor Deng Qingyun of Kodak in 1987 is equal to use sandwich device architecture in patent US4356429, develops
OLED device light emission luminance under 10V direct voltage drive reaches 1000cd/m2, OLED is made to obtain epoch-making development.?
In past 20 years, using novel light-emitting body, the OLED device of especially organic-heavy metal complex phosphorescent emitters is obtained
No small success.However, due to more difficult acquisition band gap phosphor, can satisfy at present efficient pure blue shine (yCIE <
0.15, yCIE+xCIE < 0.30) phosphorescent emitters quantity is very rare, and relative to green and red phosphorescence material,
Selection also has comparable challenge for the material of main part with high triplet energy of blue phosphorescent.Therefore, blue phosphorus is developed
The material of main part of luminescent material has very urgent practical application request.Currently, exploitation has smaller single line with ambipolar
State-triplet difference material of main part, becoming design, efficiently the low material of main part to roll-off has great importance.Meanwhile it sending out
It is still very necessary to open up efficient, stable blue luminescence body.It, can using blue fluorescent material in view of various factors
So that the full-color display of OLED or the practical production of white-light illuminating reduce cost and simplify manufacturing process.But previous warp
The blue organic fluorescence materials of allusion quotation can be divided into n-type molecule from molecular structure, and p-type molecule, they are in device work
It shows as that electronics is leading or to show as hole leading, thus is difficult to realize the balance of carrier, so as to cause device electricity
It flows efficiency and quantum efficiency is relatively low.And Donor-Acceptor (D-A) type molecule is simply designed, although bipolarity can be able to achieve
Transmission, achievees the purpose that equilbrium carrier, but due to the Intramolecular electron transfer between electron unit and electrophilic subelement
Effect, can make the band gap of compound narrow, lead to glow peak red shift, it is difficult to obtain ideal blue-light-emitting.Overcome this
It is difficult, it is necessary to selection have receptor combination of the proper strength to electrical donor and electrophilicity at molecule, intramolecular charge
Transfer control could obtain the blue organic fluorescence materials that performance is good, excitation purity is high in certain degree.
It up to now, is sulphur dibenzofuran, phosphorus oxygen, triphen for the skeleton of the most of vapor deposition molecule of organic electro-optic device
The units such as amine are core, and are but rarely reported with the organic light emission small molecule that 9,9- diphenyl thioxanthene is core.
So far Organic Light Emitting Diode has been achieved for considerable progress, and by phosphorescence hydridization, we can be obtained
The very high white light parts of the simple efficiency of device architecture.And the efficiency of this phosphorescence hydridization device be largely dependent upon it is glimmering
The efficiency of light, therefore the efficient fluorescent material of development still has very important meaning.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing one kind contains 9,
The conjugated compound of 9- diphenyl thioxanthene.The material structure is single, and molecular weight determines, has preferable dissolubility and film forming.
Another object of the present invention is to provide the preparation methods of the conjugated compound of the above-mentioned thioxanthene of diphenyl containing 9,9-.
A further object of the present invention is to provide the conjugated compounds of the above-mentioned thioxanthene of diphenyl containing 9,9- in organic photoelectric device
Application in part.
The object of the invention is achieved through the following technical solutions:
A kind of conjugated compound of the thioxanthene Han 9,9- diphenyl, the conjugated compound for containing 9,9- diphenyl thioxanthene have
General structure shown in formula 1 or formula 2:
Wherein R1And R2For the identical or different ethylene support group with electron, acetylene support group, hydrocarbon atom structure
At aromatic rings, carbon nitrogen hydrogen atom constitute aromatic heterocycle, carbon nitrogen oxygen hydrogen atom constitute aromatic heterocycle, carbon sulphur hydrogen atom constitute
Aromatic heterocycle, carbon silicon hydrogen atom constitute aromatic heterocycle, C1~C24 alkyl, alkyl-substituted conjugate unit, alkoxy take
The simultaneously-substituted conjugate unit of conjugate unit or alkyl and alkoxy in generation.
The synthetic method of the above-mentioned conjugated compound for containing 9,9- diphenyl thioxanthene, includes the following steps:
(1) 2- bromophenyl diphenyl sulfide obtains 9,9- diphenyl thioxanthene, so with diphenylmethyl reactive ketone under n-BuLi catalysis
It is reacted afterwards with bromine, obtains bromine and replace 9,9- diphenyl thioxanthene;
(2) bromine obtained by step (1) is replaced into 9,9- diphenyl thioxanthene and R1And R2The compound of base by Suzuki be coupled,
Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, or bromine obtained by step (1) is replaced 9,9- hexichol
Base thioxanthene after hydrogen peroxide oxidation with R1And R2The compound of base is coupled by Suzuki, Buchwald-Hartwig is coupled or copper
It is catalyzed halogenated aryl hydrocarbon ammoxidation, obtains the conjugated compound of the thioxanthene Han 9,9- diphenyl.
Application of the conjugated compound of the above-mentioned thioxanthene of diphenyl containing 9,9- in organic electro-optic device.
Application of the conjugated compound of the above-mentioned thioxanthene of diphenyl containing 9,9- as organic light-emitting diode layer material.
Concrete application process includes: in the hole transmission layer (formal dress device) or electron transfer layer being located on ito glass
Made on (flip device) by the conjugated compound film of vacuum evaporation or the solution coating preparation thioxanthene of diphenyl containing 9,9-
For luminescent layer, then vapor deposition or solution coat electron transfer layer (formal dress device) on the light-emitting layer or hole transmission layer is (
Fill device), then evaporation metal electrode, obtain organic light emitting diode device.
Compared to current material and technology, the invention has the following advantages and beneficial effects:
(1) the conjugated compound structure of the thioxanthene of the invention Han 9,9- diphenyl is single, and molecular weight determines, more convenient for purification
Secondary synthesis reproducibility is good, and is convenient for research structure-performance relationship.
(2) the conjugated compound material of the thioxanthene of diphenyl containing 9,9- of the invention has lower biochemical temperature and decomposes temperature
Degree, film morphology are stablized.
(3) conjugated compound of the thioxanthene of diphenyl containing 9,9- of the invention can effectively be adjusted by changing the chemical structure of connection
Control the conjugate length and luminous color of the material.
(4) conjugated compound of the thioxanthene of the invention Han 9,9- diphenyl, which passes through, changes containing the modification group on aromatic structure,
The physical characteristic of the material and the photoelectric device performance based on it can further be improved, by comparing with material reported in the literature
It was found that the device performance of the material based on this patent obtains larger raising.
Detailed description of the invention
Absorption and emission spectra figure of the Fig. 1 for P3 used in embodiment 13 in dichloromethane solution.
Fig. 2 and Fig. 3 is respectively in embodiment 13 using Current density-voltage-brightness of the P3 as luminescent layer obtained device
Graph of relation and luminance-current efficiency-power efficiency relation curve figure.
Absorption and emission spectra figure of the Fig. 4 for P6 used in embodiment 14 in dichloromethane solution.
Fig. 5 and Fig. 6 is respectively the electric current in embodiment 14 using P6 and comparison DMAc-DPS as luminescent layer obtained device
Density vs. voltage-brightness relationship curve figure and luminance-current efficiency-power efficiency relation curve figure.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) 2- bromophenyl diphenyl sulfide (11mmol, 2.93g) is dissolved in the anhydrous THF of 60ml, is cooled to -78 DEG C, is added dropwise to
N-BuLi (14.36mmol) keeps the temperature 1 hour, benzophenone (10mmol, 3.38g) is dissolved in 30mlTHF, reaction is added drop-wise to
System, overnight.It is extracted with dichloromethane, it is dry, silica gel chromatographic column is crossed, white solid is obtained.Ice vinegar is directly added by what is obtained
It in acid, is heated to reflux, 15ml concentrated hydrochloric acid is added, generate solid precipitating, suction filtration obtains white solid product M1 (2.7g, yield
50%).1HNMR:7.43-7.45(d,2H),7.37-7.40(d,4H),7.17-7.23(m,6H),6.87-6.90(d,4H),
6.62- 6.65(d,2H)。
(2) M1 (2.7g, 7.7mmol) is dissolved in the glacial acetic acid of 50mL, is heated to reflux.The liquid of 2 times of molar equivalents is added
Bromine, reaction is overnight.It is extracted with dichloromethane, washes, it is dry, solvent is removed under reduced pressure and obtains white solid M2, yield 90%.1HNMR:7.43-7.45(d,2H),7.37-7.40(d,4H),7.17- 7.23(m,4H),6.87-6.90(d,4H),6.62-
6.65(d,2H)。
(3) M2 and 50mL glacial acetic acid is added in 100mL there-necked flask, after stirring, 30% hydrogen peroxide of 10mL is added, adds
Ethyl alcohol is added after cooling overnight in heat reflux, filters, solvent is removed under reduced pressure and obtains white solid M3, yield 97%.1HNMR:
8.33-8.34(d,2H),8.14-8.16(d,4H),7.17-7.23(m, 4H),6.87-6.90(d,4H),6.62-6.65(d,
2H)。
The present embodiment reaction process is shown below:
Embodiment 2
(1) by M2 (1.5mmol, 0.81g), carbazole (3.3ml, 0.57g), CuI (0.23g), K2CO3(0.55 g), C18O6
(0.1g) is dissolved in DMPU, is heated 180 DEG C, overnight, is extracted with dichloromethane, dry, extraction, is crossed column and is obtained 0.83g containing 9,9-
The conjugated compound P1 of diphenyl thioxanthene, yield 82%.1HNMR: 8.33-8.34(d,2H),8.14-8.16(d,4H),
7.65-7.67(d,4H),7.56-7.58(d,4H),5.49-5.51(d, 4H),7.41-7.44(d,4H),7.29-7.31(m,
6H),7.17-7.18(d,4H)。
(2) by M3 (1.5mmol, 0.81g), carbazole (3.3ml, 0.57g), CuI (0.23g), K2CO3(0.55 g), C18O6
(0.1g) is dissolved in DMPU, is heated 180 DEG C, overnight, is extracted with dichloromethane, dry, extraction, is crossed column and is obtained 0.83g containing 9,9-
The conjugated compound P2 of diphenyl thioxanthene, yield 80%.1HNMR: 8.85-8.84(d,2H),8.14-8.16(d,4H),
7.65-7.67(d,4H),7.56-7.58(d,4H),5.49-5.51(d, 4H),7.41-7.44(d,4H),7.29-7.31(m,
6H),7.17-7.18(d,4H)。
The present embodiment reaction process is shown below:
Embodiment 3
(1) by M2 (1.5mmol, 0.81g), tert-butyl carbazole (3.3ml, 0.92g), CuI (0.23g), K2CO3
(0.55g), C18O6(0.1g) is dissolved in DMPU, is heated 180 DEG C, overnight, is extracted with dichloromethane, and dry, extraction is crossed column and obtained
The conjugated compound P3 of 0.83g thioxanthene Han 9,9- diphenyl, yield 82%.
(2) by M3 (1.5mmol, 0.81g), carbazole (3.3ml, 0.57g), CuI (0.23g), K2CO3(0.55 g), C18O6
(0.1g) is dissolved in DMPU, is heated 180 DEG C, overnight, is extracted with dichloromethane, dry, extraction, is crossed column and is obtained 0.83g containing 9,9-
The conjugated compound P4 of diphenyl thioxanthene, yield 80%.1HNMR: 8.85-8.84(d,2H),8.14-8.16(d,4H),
7.65-7.67(d,4H),7.56-7.58(d,4H),5.49-5.51(d, 4H),7.41-7.44(d,4H),7.29-7.31(m,
4H),7.17-7.18(d,4H),1.43(d,18H)。
The present embodiment reaction process is shown below:
Embodiment 4
(1) by M2 (1.5mmol, 0.81g), acridine (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60 millis
Gram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.It is cold
But after, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, after separation
Solvent is removed, white solid is obtained with silica gel chromatographic column separating-purifying, obtains high-purity in sublimed under vacuum after drying
The conjugated compound P5 (1.24g, yield 86%) of the diphenyl thioxanthene containing 9,9-.
(2) by M3 (1.5mmol, 0.81g), acridine (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60 millis
Gram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.It is cold
But after, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, after separation
Solvent is removed, white solid is obtained with silica gel chromatographic column separating-purifying, obtains high-purity in sublimed under vacuum after drying
The conjugated compound P6 (1.26g, yield 87%) of the diphenyl thioxanthene containing 9,9-.
The present embodiment reaction process is shown below:
Embodiment 5
(1) by M2 (1.5mmol, 0.81g), phenoxazine (3.5ml, 0.68g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P7 (1.21g, yield 85%) of the thioxanthene Han 9,9- diphenyl.
(2) by M3 (1.5mmol, 0.81g), phenoxazine (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P8 (1.22g, yield 83%) of the thioxanthene Han 9,9- diphenyl.
The present embodiment reaction process is shown below:
Embodiment 6
(1) by M2 (1.5mmol, 0.81g), phenthazine (3.5ml, 0.68g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P9 (1.21g, yield 85%) of the thioxanthene Han 9,9- diphenyl.
(2) by M3 (1.5mmol, 0.81g), phenthazine (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P10 (1.22g, yield 83%) of the thioxanthene Han 9,9- diphenyl.
The present embodiment reaction process is shown below:
Embodiment 7
(1) by M2 (1.5mmol, 0.81g), diphenylamines (3.5ml, 0.68g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P11 (1.20g, yield 86%) of the thioxanthene Han 9,9- diphenyl.
(2) by M3 (1.5mmol, 0.81g), diphenylamines (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60
Milligram palladium acetate, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24 hours.
After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation
After remove solvent, obtain white solid with silica gel chromatographic column separating-purifying, obtained after drying in sublimed under vacuum high-purity
Spend the conjugated compound P12 (1.22g, yield 85%) of the thioxanthene Han 9,9- diphenyl.
The present embodiment reaction process is shown below:
Embodiment 8
(1) by M2 (1.5mmol, 0.81g), tert-butyl diphenylamine (3.5ml, 1.0g), 100 milliliters of first as solvent
Benzene, 60 milligrams of palladium acetates, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24
Hour.After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate drying is organic
Phase removes solvent after separation, obtains white solid with silica gel chromatographic column separating-purifying, obtains after drying in sublimed under vacuum
To the conjugated compound P13 (1.19g, yield 82%) of high-purity thioxanthene Han 9,9- diphenyl.
(2) by M3 (1.5mmol, 0.81g), tert-butyl diphenylamine (3.5ml, 1.0g), 100 milliliters of first as solvent
Benzene, 60 milligrams of palladium acetates, tri-tert phosphorus (0.5mmol, 0.11g) and 0.75 gram of potassium carbonate.It is heated to reflux down and is stirred to react 24
Hour.After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate drying is organic
Phase removes solvent after separation, obtains white solid with silica gel chromatographic column separating-purifying, obtains after drying in sublimed under vacuum
To the conjugated compound P14 (1.22g, yield 83%) of high-purity thioxanthene Han 9,9- diphenyl.
The present embodiment reaction process is shown below:
Embodiment 9
(1) by M2 (1.08g, 3.5mmol) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3, penta boron of 2- dioxa
Alkane -2- base) aniline (2.6g, 7mmol) is added in 250ml single-necked flask, 120ml toluene, 40ml ethyl alcohol and 30ml is added
Then the triphenylphosphine zeroth order palladium of 100mg is added in the wet chemical of 2M, ventilate half an hour, displace in reaction system
Oxygen, ventilation finish sealing, and 90-100 DEG C of heating is reacted 18-24 hours, and cooling, methylene chloride extraction, organic phase is dry, too short
Column, petroleum ether: methylene chloride=5:1 crosses column, obtains white solid product P15 (3.6g, yield 90%).
(2) by M3 (1.08g, 3.5mmol) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3, penta boron of 2- dioxa
Alkane -2- base) aniline (2.6g, 7mmol) is added in 250ml single-necked flask, 120ml toluene, 40ml ethyl alcohol and 30ml is added
Then the triphenylphosphine zeroth order palladium of 100mg is added in the wet chemical of 2M, ventilate half an hour, displace in reaction system
Oxygen, ventilation finish sealing, and 90-100 DEG C of heating is reacted 18-24 hours, and cooling, methylene chloride extraction, organic phase is dry, too short
Column, petroleum ether: methylene chloride=1:1 crosses column, obtains white solid product P16 (3.70g, yield 92%).
The present embodiment reaction process is shown below:
Embodiment 10
(1) by M2 (1.08g, 3.5mmol) and 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -
2- yl) carbazole (2.6g, 7mmol) is added in 250ml single-necked flask, 120ml toluene, 40ml ethyl alcohol and 30ml 2M is added
Then the triphenylphosphine zeroth order palladium of 100mg is added in wet chemical, ventilate half an hour, displace the oxygen in reaction system,
Ventilation finishes sealing, and 90-100 DEG C of heating is reacted 18-24 hours, and cooling, methylene chloride extraction, organic phase is dry, crosses short column,
Petroleum ether: methylene chloride=5:1 crosses column, obtains white solid product P17 (3.6g, yield 90%).
(2) by M3 (1.08g, 3.5mmol) and 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -
2- yl) carbazole (2.6g 7mmol) is added in 250ml single-necked flask, 120ml toluene, 40ml ethyl alcohol and 30ml 2M is added
Then the triphenylphosphine zeroth order palladium of 100mg is added in wet chemical, ventilate half an hour, displace the oxygen in reaction system,
Ventilation finishes sealing, and 90-100 DEG C of heating is reacted 18-24 hours, and cooling, methylene chloride extraction, organic phase is dry, crosses short column,
Petroleum ether: methylene chloride=1:1 crosses column, obtains white solid product P18 (3.70g, yield 92%).
The present embodiment reaction process is shown below:
Embodiment 11
(1) 250ml single-necked flask is added to by M2 (1.08g, 3.5mmol) and to carbazole borate ester (2.6g, 7mmol)
In, the wet chemical of 120ml toluene, 40ml ethyl alcohol and 30ml 2M is added, the triphenylphosphine zeroth order of 100mg is then added
Palladium is ventilated half an hour, and the oxygen in reaction system is displaced, and ventilation finishes sealing, and 90-100 DEG C of heating is reacted 18-24 hours,
Cooling, methylene chloride extraction, organic phase is dry, crosses short column, petroleum ether: methylene chloride=5:1 crosses column, obtains white solid product
P19 (3.6g, yield 90%).
(2) M3 (1.08g, 3.5mmol) is added to 250 ml single-necked flasks to carbazole borate ester (2.6g 7mmol)
In, the wet chemical of 120ml toluene, 40ml ethyl alcohol and 30ml 2M is added, the triphenylphosphine zeroth order of 100mg is then added
Palladium is ventilated half an hour, and the oxygen in reaction system is displaced, and ventilation finishes sealing, and 90-100 DEG C of heating is reacted 18-24 hours,
Cooling, methylene chloride extraction, organic phase is dry, crosses short column, petroleum ether: methylene chloride=1:1 crosses column, obtains white solid product
P20 (3.70g, yield 92%).
The present embodiment reaction process is shown below:
Embodiment 12
(1) in a nitrogen atmosphere, M2 (1.25g, 3.5mmol) is added into 100ml flask, 15ml nitrogen nitrogen dimethyl second
Alkenyl urea, cuprous iodide (0.56g), potassium carbonate (1.40g), 9- hydrogen -3-9 '-bis- carbazoles (7.2mmol, 2.4g), 18- crown ether -
6 0.21g are stirred to react 24 hours at 160 DEG C.It is extracted with dichloromethane, liquid separation, merges organic phase, it is dry with anhydrous magnesium sulfate
It is dry, it filters, resulting filtrate removes solvent under reduced pressure, and post separation obtains white product, rises under vacuum after drying
China obtains the conjugated compound P21 (1.63g, yield 56%) of high-purity thioxanthene Han 9,9- diphenyl.
(2) in a nitrogen atmosphere, M3 (1.25g, 3.5mmol) is added into 100ml flask, 15ml nitrogen nitrogen dimethyl second
Alkenyl urea, cuprous iodide (0.56g), potassium carbonate (1.40g), 9- hydrogen -3-9 '-bis- carbazoles (7.2mmol, 2.4g), 18- crown ether -
6 0.21g are stirred to react 24 hours at 160 DEG C.It is extracted with dichloromethane, liquid separation, merges organic phase, it is dry with anhydrous magnesium sulfate
It is dry, it filters, resulting filtrate removes solvent under reduced pressure, and post separation obtains white product, rises under vacuum after drying
China obtains the conjugated compound P22 (1.63g, yield 56%) of high-purity thioxanthene Han 9,9- diphenyl.
The present embodiment reaction process is shown below:
Embodiment 13
Preparation and photoelectric properties of the present embodiment using P3 as Organic Light Emitting Diode (OLED) device of luminescent layer are surveyed
Test result:
Ito glass is handled after ultrasonic cleaning with oxygen-Plasma, and the square resistance of ito glass is 10 Ω/cm2。
Hole injection layer is HAT-CN, and hole transmission layer is NPB and TCTA, and luminescent layer, which uses, contains 9,9- bis- obtained by the embodiment of the present invention 3
The conjugated compound P3 of phenylthioxanthen, electron transfer layer use TPBI.Cathode electrode uses LiF/Al metal.ITO and metal electricity
Interpolar applies positive bias, and the characteristic of device is tested under different electric currents.
NPB refers to that N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines, TCTA refer to 4,4', 4 "-three
(carbazole -9- base) triphenylamine, TPBI refer to 1,3,5- tri- (1- phenyl -1-H- benzo [d] imidazoles -2-) benzene.Structure is as follows:
Absorption and emission spectra figure of the P3 used in the present embodiment in dichloromethane solution is as shown in Figure 1.Using P3 conduct
The Current density-voltage of luminescent layer obtained device-brightness relationship curve figure and luminance-current efficiency-power efficiency relation curve
Figure is as shown in Figures 2 and 3 respectively.Obtained device photoelectric properties test data such as table 1:
Table 1
Embodiment 14
Preparation and photoelectric properties of the present embodiment using P6 as Organic Light Emitting Diode (OLED) device of luminescent layer are surveyed
Test result:
Ito glass is handled after ultrasonic cleaning with oxygen-Plasma, and the square resistance of ito glass is 10 Ω/cm2。
Hole injection layer is TAPC, and luminescent layer is mixed using the conjugated compound P6 of the thioxanthene Han 9,9- diphenyl obtained by the embodiment of the present invention 4
It is miscellaneous in main body DPEPO, electron transfer layer use DPEPO and TmPyPB.Cathode electrode uses LiF/Al metal.ITO and metal
Apply positive bias between electrode, the characteristic of device is tested under different electric currents.Comparative device is DMAc-DPS and DMTDAc.
TAPC refers to 4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline], and TmPyPB refers to 1,3,5- tri- [(3- hexichol
Base) -3- phenyl] benzene, DPEPO refers to two [2- ((oxo) diphenylphosphino) phenyl] ethers.Structure is as follows:
Absorption and emission spectra figure of the P6 used in the present embodiment in dichloromethane solution is as shown in Figure 4.Using P6 and right
Current density-voltage-brightness relationship curve figure and luminance-current efficiency-function than DMAc-DPS as luminescent layer obtained device
Rate relationship between efficiency curve graph difference is as shown in Figure 5 and Figure 6.Obtained device photoelectric properties test data such as table 2:
Table 2
As can be seen from the above results, the conjugated compound of present invention gained thioxanthene Han 9,9- diphenyl is compared to existing
DMAc-DPS and DMTDAc material is obviously improved as the external quantum efficiency of the OLED device of luminescent layer.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (4)
1. a kind of conjugated compound of the thioxanthene Han 9,9- diphenyl, it is characterised in that the conjugation for containing 9,9- diphenyl thioxanthene
Closing object has general structure shown in formula 1 or formula 2:
Wherein R1And R2It is constituted for the identical or different ethylene support group with electron, acetylene support group, hydrocarbon atom
The virtue that aromatic heterocycle, the carbon sulphur hydrogen atom of aromatic heterocycle, carbon nitrogen oxygen hydrogen atom composition that aromatic rings, carbon nitrogen hydrogen atom are constituted are constituted
Fragrant heterocycle, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the alkyl of C1~C24, alkyl-substituted conjugate unit, alkoxy replace
Conjugate unit or the simultaneously-substituted conjugate unit of alkyl and alkoxy.
2. the synthetic method of the conjugated compound of one kind thioxanthene Han 9,9- diphenyl described in claim 1, it is characterised in that packet
Include following steps:
(1) 2- bromophenyl diphenyl sulfide n-BuLi catalysis under with diphenylmethyl reactive ketone, obtain 9,9- diphenyl thioxanthene, then with
Bromine reaction obtains bromine and replaces 9,9- diphenyl thioxanthene;
(2) bromine obtained by step (1) is replaced into 9,9- diphenyl thioxanthene and R1And R2The compound of base by Suzuki be coupled,
Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, or bromine obtained by step (1) is replaced 9,9- hexichol
Base thioxanthene after hydrogen peroxide oxidation with R1And R2The compound of base is coupled by Suzuki, Buchwald-Hartwig is coupled or copper
It is catalyzed halogenated aryl hydrocarbon ammoxidation, obtains the conjugated compound of the thioxanthene Han 9,9- diphenyl.
3. application of the conjugated compound of the thioxanthene of diphenyl containing 9,9- described in claim 1 in organic electro-optic device.
4. application of the conjugated compound according to claim 3 for containing 9,9- diphenyl thioxanthene in organic electro-optic device,
It is characterized in that concrete application process includes: to pass through vacuum evaporation or molten on the hole transmission layer being located on ito glass
Then the conjugated compound film of liquid coating preparation thioxanthene Han 9,9- diphenyl is deposited or molten on the light-emitting layer as luminescent layer
Liquid coats electron transfer layer, then evaporation metal electrode, obtains Organic Light Emitting Diode formal dress device;Or on being located at ito glass
Electron transfer layer on by vacuum evaporation or solution coating preparation the thioxanthene of diphenyl containing 9,9- conjugated compound film
As luminescent layer, then vapor deposition or solution coat hole transmission layer, then evaporation metal electrode on the light-emitting layer, obtain organic hair
Optical diode flip device.
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CN108264479A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | A kind of organic electroluminescence device |
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CN108264479A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | A kind of organic electroluminescence device |
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