CN109134524A - The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application - Google Patents
The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application Download PDFInfo
- Publication number
- CN109134524A CN109134524A CN201810870598.8A CN201810870598A CN109134524A CN 109134524 A CN109134524 A CN 109134524A CN 201810870598 A CN201810870598 A CN 201810870598A CN 109134524 A CN109134524 A CN 109134524A
- Authority
- CN
- China
- Prior art keywords
- thia
- dibenzo
- silacyclohexadiene
- conjugated compound
- hydrogen atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
Abstract
The invention belongs to electroluminescent material technical fields, disclose conjugated compound and the preparation and application of one kind thia silacyclohexadiene Han 9,9- dibenzo.The conjugated compound for containing 9,9- dibenzo thia silacyclohexadiene 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 one kind contains 9,9- dibenzo thia sila hexamethylene two
The conjugated compound of alkene 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 it is previous classical
Blue organic fluorescence materials can be divided into n-type molecule from molecular structure, p-type molecule, they want 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 current
Efficiency and quantum efficiency are relatively low.And Donor-Acceptor (D-A) type molecule is simply designed, although bipolarity biography can be able to achieve
It is defeated, achieve the purpose that equilbrium carrier, but since the Intramolecular electron transfer between electron unit and electrophilic subelement is made
With the band gap of compound can be made to narrow, lead to glow peak red shift, it is difficult to obtain ideal blue-light-emitting.Overcome this tired
It is difficult, it is necessary to selection have receptor combination of the proper strength to electrical donor and electrophilicity at molecule, intramolecular charge is turned
Control is moved in certain degree, the blue organic fluorescence materials that performance is good, excitation purity is high could be obtained.
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- dibenzo thia silacyclohexadiene 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- dibenzo thia silacyclohexadiene.The material structure is single, and molecular weight determines, has preferable dissolution
Property and film forming.
Another object of the present invention is to provide the conjugated compounds of the above-mentioned thia of dibenzo containing 9,9- silacyclohexadiene
Preparation method.
A further object of the present invention is to provide the conjugated compounds of the above-mentioned thia of dibenzo containing 9,9- silacyclohexadiene
Application in organic electro-optic device.
The object of the invention is achieved through the following technical solutions:
A kind of conjugated compound of the thia silacyclohexadiene Han 9,9- dibenzo, it is described to contain 9,9- dibenzo thia sila
The conjugated compound of cyclohexadiene has the general structure as shown in following 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- dibenzo thia silacyclohexadiene, includes the following steps:
(1) 2- bromophenyl diphenyl sulfide reacts under n-BuLi catalysis with diphenyl chlorosilane, obtains 9,9- dibenzo thia
Then silacyclohexadiene is reacted with bromine, obtain bromine and replace 9,9- dibenzo thia silacyclohexadiene；
(2) bromine obtained by step (1) is replaced into 9,9- dibenzo thia silacyclohexadiene and R1And R2The compound of base passes through
Suzuki coupling, Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, or bromine obtained by step (1) is taken
For 9,9- dibenzo thia silacyclohexadiene after hydrogen peroxide oxidation with R1And R2The compound of base by Suzuki be coupled,
Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, obtain the sila ring containing 9,9- dibenzo thia
The conjugated compound of hexadiene.
Application of the conjugated compound of the above-mentioned thia of dibenzo containing 9,9- silacyclohexadiene in organic electro-optic device.
The conjugated compound of the above-mentioned thia of dibenzo containing 9,9- silacyclohexadiene is as organic light-emitting diode layer
The application of material.
Concrete application process includes: in the hole transmission layer (formal dress device) or electron transfer layer being located on ito glass
Pass through vacuum evaporation or the conjugation of the solution coating preparation thia of dibenzo containing 9,9- silacyclohexadiene on (flip device)
Compound film is as luminescent layer, then vapor deposition or solution coating electron transfer layer (formal dress device) or empty on the light-emitting layer
Cave transport layer (flip 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 thia silacyclohexadiene of the invention Han 9,9- dibenzo is single, and molecular weight determines,
Convenient for purification, multi-stage synthesis reproducibility is good, and is convenient for research structure-performance relationship.
(2) the conjugated compound material of the thia silacyclohexadiene of dibenzo containing 9,9- of the invention has lower biochemical temperature
Degree and decomposition temperature, film morphology are stablized.
(3) conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- of the invention can be by changing the chemistry connected
Structure effectively regulates and controls the conjugate length and luminous color of the material.
(4) conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- of the invention is by changing containing on aromatic structure
Modification group, can further improve the physical characteristic of the material and the photoelectric device performance based on it, by with document report
The material in road compares discovery, and 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 (29mmol) keeps the temperature 1 hour, diphenyl chlorosilane (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, heats
Ethyl alcohol is added after cooling overnight in 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(0.55g), 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 dibenzo thia silacyclohexadiene, 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(0.55g), 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 dibenzo thia silacyclohexadiene, 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 thia silacyclohexadiene Han 9,9- dibenzo, 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, 4H), 7.17-7.18 (d, 4H), 1.43 (d, 18H).
(2) by M3 (1.5mmol, 0.81g), carbazole (3.3ml, 0.57g), CuI (0.23g), K2CO3(0.55g), 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 dibenzo thia silacyclohexadiene, 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 milligrams
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 cooling
Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, goes after separation
Except solvent, white solid is obtained with silica gel chromatographic column separating-purifying, high-purity is obtained in sublimed under vacuum after drying and contains
The conjugated compound P5 (1.24g, yield 86%) of 9,9- dibenzo thia silacyclohexadienes.
(2) by M3 (1.5mmol, 0.81g), acridine (3.5ml, 0.72g), as 100 milliliters of toluene of solvent, 60 milligrams
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 cooling
Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, goes after separation
Except solvent, white solid is obtained with silica gel chromatographic column separating-purifying, high-purity is obtained in sublimed under vacuum after drying and contains
The conjugated compound P6 (1.26g, yield 87%) of 9,9- dibenzo thia silacyclohexadienes.
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 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 P7 (1.21g, yield 85%) of the dibenzo thia silacyclohexadiene containing 9,9-.
(2) by M3 (1.5mmol, 0.81g), phenoxazine (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 P8 (1.22g, yield 83%) of the dibenzo thia silacyclohexadiene containing 9,9-.
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 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 P9 (1.21g, yield 85%) of the dibenzo thia silacyclohexadiene containing 9,9-.
(2) by M3 (1.5mmol, 0.81g), phenthazine (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 P10 (1.22g, yield 83%) of the dibenzo thia silacyclohexadiene containing 9,9-.
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 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 P11 (1.20g, yield 86%) of the dibenzo thia silacyclohexadiene containing 9,9-.
(2) by M3 (1.5mmol, 0.81g), diphenylamines (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 P12 (1.22g, yield 85%) of the dibenzo thia silacyclohexadiene containing 9,9-.
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 thia silacyclohexadiene Han 9,9- dibenzo.
(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 thia silacyclohexadiene Han 9,9- dibenzo.
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 2M is added
Wet chemical, then be added 100mg triphenylphosphine zeroth order palladium, ventilate half an hour, displace the oxygen in reaction system
Gas, 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 2M is added
Wet chemical, then be added 100mg triphenylphosphine zeroth order palladium, ventilate half an hour, displace the oxygen in reaction system
Gas, 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, stone
Oily 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, stone
Oily 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 250ml single-necked flask 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 dimethylvinylsiloxy
Base 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 is 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 thia silacyclohexadiene Han 9,9- dibenzo.
(2) in a nitrogen atmosphere, M3 (1.25g, 3.5mmol) is added into 100ml flask, 15ml nitrogen nitrogen dimethylvinylsiloxy
Base 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 is 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 thia silacyclohexadiene Han 9,9- dibenzo.
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 benzo thia silacyclohexadiene, electron transfer layer use TPBI.Cathode electrode uses LiF/Al metal.
Apply positive bias between ITO and metal electrode, 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 total to using the thia silacyclohexadiene Han 9,9- dibenzo obtained by the embodiment of the present invention 4
Compound conjugate P6 is entrained in main body DPEPO, and electron transfer layer uses DPEPO and TmPyPB.Cathode electrode is using LiF/Al gold
Belong to.Apply positive bias between ITO and metal electrode, the characteristic of device is tested under different electric currents.Comparative device be 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 thia silacyclohexadiene Han 9,9- dibenzo
The external quantum efficiency of OLED device compared to existing DMAc-DPS and DMTDAc material as luminescent layer is obviously improved.
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 thia silacyclohexadiene Han 9,9- dibenzo, it is characterised in that described to contain 9,9- dibenzo
The conjugated compound of thia silacyclohexadiene has the general structure as shown in following 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 thia silacyclohexadiene Han 9,9- dibenzo described in claim 1,
It is characterized by comprising following steps:
(1) 2- bromophenyl diphenyl sulfide reacts under n-BuLi catalysis with diphenyl chlorosilane, obtains 9,9- dibenzo thia sila
Then cyclohexadiene is reacted with bromine, obtain bromine and replace 9,9- dibenzo thia silacyclohexadiene；
(2) bromine obtained by step (1) is replaced into 9,9- dibenzo thia silacyclohexadiene and R1And R2The compound of base passes through
Suzuki coupling, Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, or bromine obtained by step (1) is taken
For 9,9- dibenzo thia silacyclohexadiene after hydrogen peroxide oxidation with R1And R2The compound of base by Suzuki be coupled,
Buchwald-Hartwig coupling or copper are catalyzed halogenated aryl hydrocarbon ammoxidation, obtain the sila ring containing 9,9- dibenzo thia
The conjugated compound of hexadiene.
3. the conjugated compound of the thia of dibenzo containing 9,9- silacyclohexadiene described in claim 1 is in organic electro-optic device
Application.
4. the conjugated compound of the thia of dibenzo containing 9,9- silacyclohexadiene according to claim 3 is in organic photoelectric device
Application in part, it is characterised in that concrete application process includes: to pass through vacuum on the hole transmission layer being located on ito glass
The conjugated compound film of vapor deposition or solution coating preparation the thia silacyclohexadiene Han 9,9- dibenzo is as luminescent layer, so
Vapor deposition or solution coat electron transfer layer, then evaporation metal electrode on the light-emitting layer afterwards, obtain Organic Light Emitting Diode formal dress
Device；Or hexichol containing 9,9- is prepared by vacuum evaporation or solution coating on the electron transfer layer being located on ito glass
And the conjugated compound film of thia silacyclohexadiene, as luminescent layer, then vapor deposition or solution coating are empty on the light-emitting layer
Cave transport layer, then evaporation metal electrode, obtain Organic Light Emitting Diode flip device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870598.8A CN109134524A (en) | 2018-08-02 | 2018-08-02 | The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870598.8A CN109134524A (en) | 2018-08-02 | 2018-08-02 | The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109134524A true CN109134524A (en) | 2019-01-04 |
Family
ID=64798633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810870598.8A Pending CN109134524A (en) | 2018-08-02 | 2018-08-02 | The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109134524A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154067A (en) * | 2015-09-01 | 2015-12-16 | 华南理工大学 | Spiro-di-thioxanthene-based small-molecule luminescent material and preparation and application thereof |
| CN108264479A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | A kind of organic electroluminescence device |
-
2018
- 2018-08-02 CN CN201810870598.8A patent/CN109134524A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154067A (en) * | 2015-09-01 | 2015-12-16 | 华南理工大学 | Spiro-di-thioxanthene-based small-molecule luminescent material and preparation and application thereof |
| CN108264479A (en) * | 2016-12-30 | 2018-07-10 | 昆山国显光电有限公司 | A kind of organic electroluminescence device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104844587B (en) | Conjugated compound containing phenoxazine thiophene structure and preparation method thereof and organic electroluminescent diode apparatus | |
| CN108976244A (en) | The compound of the formula thioxanthene of spiral shell containing 9,9- and preparation and application | |
| KR101558966B1 (en) | Asymmetric ortho-Terphenyl Derivatives and Organic light emitting device Comprising the Same | |
| TWI465441B (en) | Imidazole derivatives having vinyl group and its use in electroluminescent element | |
| JP4746492B2 (en) | Synthesis method | |
| CN108864139A (en) | The conjugated compound of the formula carboline thioxanthene of spiral shell containing 9,9- and preparation and application | |
| CN112625042A (en) | Organic electroluminescent material and application thereof | |
| CN109503427A (en) | A kind of organic blue fluorescent material of D-A type and its preparation method and application | |
| CN109897029B (en) | Terpyridyl derivative, and preparation method, application and device thereof | |
| CN105601557B (en) | Containing anthracene compound, preparation method and its application, organic luminescent device | |
| CN110003115B (en) | Blue organic luminescent material, luminescent device and preparation method | |
| CN109180663A (en) | The conjugated compound of the base thioxanthene of diimidazole containing 9,9- and preparation and application | |
| CN109134524A (en) | The conjugated compound of the thia silacyclohexadiene of dibenzo containing 9,9- and preparation and application | |
| CN108976220A (en) | The conjugated compound of the formula dibenzo heptene thioxanthene of spiral shell containing 9,9- and preparation and application | |
| CN109180665A (en) | The conjugated compound of the thioxanthene of diphenyl containing 9,9- and preparation and application | |
| CN113816909A (en) | Organic electroluminescent material containing phenanthrene structure and device thereof | |
| CN109180664A (en) | The conjugated compound of the thioxanthene of pyridyl group containing 9,9- and preparation and application | |
| CN113248519A (en) | Organic compound and organic light-emitting device using same | |
| KR20100005903A (en) | Phenyl-naphthyl derivatives and organic electroluminescence light emitting diodes using the same | |
| CN112062753A (en) | Organic compound, organic photoelectric element using same and application | |
| CN111072695B (en) | Organic small molecular material containing boron-containing azanaphthalene and preparation method and application thereof | |
| CN113105382B (en) | Biphenyl modified carbazole group anthracene-based deep blue light material and preparation and application thereof | |
| CN116375708B (en) | Organic electroluminescent material based on indolospiroacridine and application of organic electroluminescent material in OLED | |
| CN113248476B (en) | Organic compound and organic light-emitting device using same | |
| CN114751890B (en) | Organic compound based on binaphthyl amine derivative and organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190104 |