CN109206422A - Bipolarity compound and its preparation method and application based on 1,3,4- thiadiazoles - Google Patents

Bipolarity compound and its preparation method and application based on 1,3,4- thiadiazoles Download PDF

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CN109206422A
CN109206422A CN201811131512.6A CN201811131512A CN109206422A CN 109206422 A CN109206422 A CN 109206422A CN 201811131512 A CN201811131512 A CN 201811131512A CN 109206422 A CN109206422 A CN 109206422A
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thiadiazoles
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CN109206422B (en
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穆广园
庄少卿
任春婷
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Hubei Shang Shang photoelectric material Co., Ltd.
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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Abstract

For the present invention with very strong 1,3, the 4- thiadiazoles for drawing electronic capability, for core group, at its 2,5, respectively with arlydene for π bridge, connection has electronics confession/acceptor ability group, being formed a kind of novel has ambipolar compound.1,3, the electronic capability of haling of this mother nucleus structure symmetry of 4- thiadiazoles makes the compound extended through π bridge that orderly close-packed structure be presented, the certain rigidity of compound is imparted with ambipolar benzheterocycle, low optical losses caused by light can be achieved near the cathode, light extraction efficiency is improved, is a kind of ideal photosphere material out.Simultaneously, since compound has the parent nucleus for haling electronics and confession/acceptor groups, make it have stronger charge balance ability, the conjugacy that π bridge interrupts, which is effectively improved band gap caused by electron and electron-withdrawing group Intramolecular electron transfer, reduces problem, device is assigned with the landing of lower driving voltage, higher device efficiency and lesser efficiency, is also a kind of excellent luminescent layer material of main part.

Description

Bipolarity compound and its preparation method and application based on 1,3,4- thiadiazoles
Technical field
The invention belongs to photoelectric material applicating technology fields, and in particular to be based on the bipolarity chemical combination of 1,3,4- thiadiazoles Object and its preparation method and application.
Background technique
OLED, i.e. Organic Light Emitting Diode, also known as Organic Electricity laser display (OLED).OLED has self luminous spy Property, the very thin coating of organic material of use and glass substrate, when an electric current passes through it, organic material will shine, and OLED Show that screen visible angle is big, and electric energy can be saved significantly on, thus OLED be considered as 21 century most future product it One.
Electroluminescent organic material mainly has three categories: small molecular organic compounds, polymer and oligomer.Small molecule Organic compound and polymer are electroluminescent organic materials most widely used at present, and polymer material generally passes through dissolution Spin coating prepares organic electroluminescence device, and rigid conjugated system main chain poor solubility occupies the majority, and HOMO is poor with lumo energy Narrow, small molecule series material is because synthesis technology is simple, level-density parameter degree is frequently used for organic electroluminescence device well Preparation.
Due to chemical structure and level characteristic, it is a certain that most of Organic micromolecular semiconductor materials are all partial to transmission Carrier (electronics or hole), and the transmittability of corresponding another carrier is then lower, small organic molecule is bipolar Property material due to having the function of the concentration in electronics and hole in balancing device, simplifying device architecture, control exciton recombination region etc. And become research hotspot in recent years, to improve the efficiency and stability of organic electroluminescence device.
In addition, organic electroluminescence device is multilayer sandwiched formula double carriers direct current injection type device, therefore device architecture The properties such as the driving voltage of device, luminous efficiency and device lifetime are had a major impact.Organic electroluminescence device Common structure be anode-single-layer or multi-layer organic functional thin film-cathode, due to refractive index phase between cathode and cover-plate glass Difference is larger, and by cathode strong reflection loss can occur for the light of OLED, therefore, how to be designed by structure, reduces light in device Internal dissipation, improve light extraction efficiency it is low be the field OLED problem to be solved.
Summary of the invention
In view of the above problems, the purpose of the present invention is to provide a kind of new bipolaritys based on 1,3,4- thiadiazoles Object is closed, and is applied to organic illuminating element, improves the efficiency and stability of organic illuminating element, solves light in organic hair The internal loss problem of optical element improves its light extraction efficiency.
First aspect of the present invention provides the bipolarity compound based on 1,3,4- thiadiazoles, and general structure is following (I) It is shown:
Wherein, Ar1、Ar2Independently are as follows: any one of the arlydene that substituted or unsubstituted carbon number is 6 to 24, Ar1、Ar2It is identical or different；
R1、R2、R3、R4、R5、R6、R7、R8Independently are as follows: the alkane that alkyl that hydrogen, carbon number are 1 to 4, carbon number are 1 to 4 Aryl that aryloxy group that oxygroup, substituted or unsubstituted carbon number are 6 to 12, substituted or unsubstituted carbon number are 6 to 12 replaces Or any one of the heterocycle that unsubstituted carbon number is 5 to 12, R1、R2、R3、R4、R5、R6、R7、R8It is identical or different；
X1、X2Independently are as follows: S, O=S=O, O or N-L；
Wherein, the L is selected from: aryl that substituted or unsubstituted carbon number is 6 to 24, substituted or unsubstituted carbon number are 6 To 24 aromatic heterocyclic, substituted or unsubstituted carbon number be 12 to 24 fluorenyl, substituted or unsubstituted carbon number be 6 to 24 Any one of aryl amine, X1、X2It is identical or different.
It should be noted that working as X1、X2Independently are as follows: when O=S=O or N-L, replace site on S or N.
As a preferred technical solution of the invention, as the Ar1、Ar2Independently are as follows: substituted carbon number is When any in 6 to 24 arlydene, the substituent group of the arlydene is selected from: alkyl that carbon number is 1 to 4, carbon number be 6 to Any one of 10 aryl；
As the R1、R2、R3、R4、R5、R6、R7、R8Independently are as follows: substituted carbon number be 6 to 12 aryloxy group, take It is the aryloxy group, described when any in the heterocycle that aryl that the carbon number in generation is 6 to 12, substituted carbon number are 5 to 12 The substituent group of aryl and the heterocycle is independently selected from: in the aryl that alkyl that carbon number is 1 to 4, carbon number are 6 to 10 It is any；
When the L is selected from: aromatic heterocyclic that aryl that substituted carbon number is 6 to 24, substituted carbon number are 6 to 24 replaces Carbon number be 12 to 24 fluorenyl, substituted carbon number be 6 to 24 aryl amine in it is any when, the aryl, the virtue are miscellaneous The substituent group of ring group, the fluorenyl and the aryl amine is independently selected from: alkyl that carbon number is 1 to 4, carbon number are 6 to 10 Any one of aryl.
As a preferred technical solution of the invention, the R1、R2、R3、R4、R5、R6、 R7、R8It is hydrogen, then it is described The general structure of bipolarity compound is shown in following (II):
As a preferred technical solution of the invention, the Ar1、Ar2Be independently selected from: it is unsubstituted, by Any one of the phenylene for the aryl substitution that is alkyl-substituted or being 6 to 10 by carbon number that carbon number is 1 to 4, unsubstituted, By any one of the biphenylene for the aryl substitution that is alkyl-substituted or being 6 to 10 by carbon number that carbon number is 1 to 4, alternatively, Any unsubstituted, in the naphthylene that by carbon number is 1 to 4 alkyl-substituted or is replaced by the aryl that carbon number is 6 to 10 Kind.
As a preferred technical solution of the invention, the X1、X2Respectively N-L, wherein the X1、X2It is corresponding L be independently selected from: it is unsubstituted, be 1 to 4 alkyl-substituted by carbon number or replaced by the aryl that carbon number is 6 to 10 Carbon number be 6 to 24 any one of aryl, it is unsubstituted, by carbon number be 1 to 4 alkyl-substituted or by carbon number be 6 to Any one of the aromatic heterocyclic that the carbon number that 10 aryl replaces is 6 to 24, alternatively, unsubstituted or be 6 to 10 by carbon number Aryl replace carbon number be 12 to 24 any one of fluorenyl.
As a preferred technical solution of the invention, the X1、X2It is independently selected from such as appointing in flowering structure It anticipates one kind:
The concrete example of the bipolarity compound based on 1,3,4- thiadiazoles as present embodiment shown in logical formula (I) Son, can enumerate structure is the bipolarity compound that 1,3,4- thiadiazoles are based on shown in compound (1) to compound (193). But the present invention is not limited to this.
The second aspect of the invention provides the preparation process of the bipolarity compound based on 1,3,4- thiadiazoles, packet Include following route:
Synthesis step are as follows:
S1, intermediate A10、Ar1The corresponding halogenated boronic acid derivatives replaced, potassium carbonate are according to molar ratio 1:(1-3): (2- 4) it feeds intake, and according to the intermediate A10: toluene: ethyl alcohol: water is that toluene, ethyl alcohol is added in 1mmol:1-4mL:1-4mL:1-4mL And water, under nitrogen protection, according to the intermediate A10Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, rise Temperature reacts 6-30h to 60-100 DEG C, and processing obtains intermediate A1；
Intermediate A20、Ar2The corresponding halogenated boronic acid derivatives replaced, potassium carbonate are according to molar ratio 1:(1-3): (2-4) is thrown Material, and according to the intermediate A20: toluene: ethyl alcohol: water be 1mmol:1-4mL:1-4mL:1-4mL be added toluene, ethyl alcohol and Water, under nitrogen protection, according to the intermediate A20Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, heating To 60-100 DEG C, 6-30h is reacted, processing obtains intermediate A2；
S2, according to the intermediate A1: tetrahydrofuran is 1mmol:2-5mL by the intermediate A1It is dissolved in tetrahydrofuran In, under nitrogen protection, -78 DEG C of stirring 0.3-2h are cooled to, by n-BuLi cyclohexane solution with itself and the intermediate A1Than Example is after 0.2-4mL:1mmol is added and reacts 0.5-3h, according to the intermediate A1Substance meter, be added 1-3 times Triethyl borate the reaction was continued 1-4h is warmed to room temperature reaction 6-20h reaction and completes, after being cooled to 0 DEG C, according to the intermediate A1: hydrochloric acid is that reaction is hydrolyzed in 1mmol:0.2-4mL addition hydrochloric acid solution, and processing obtains intermediate B1；
According to the intermediate A2: tetrahydrofuran is 1mmol:2-5mL by the intermediate A2It is dissolved in tetrahydrofuran, Under nitrogen protection, -78 DEG C of stirring 0.3-2h are cooled to, by n-BuLi cyclohexane solution with itself and the intermediate A2Ratio After being added for 0.2-4mL:1mmol and react 0.5-3h, according to the intermediate A1Substance meter, 1-3 times of boron is added Triethylenetetraminehexaacetic acid ester the reaction was continued 1-4h is warmed to room temperature reaction 6-20h reaction and completes, after being cooled to 0 DEG C, according to the intermediate A1: Hydrochloric acid is that reaction is hydrolyzed in 1mmol:0.2-4mL addition hydrochloric acid solution, and processing obtains intermediate B1；
S3, the intermediate B1, the chloro- 1,3,4- thiadiazoles of the bromo- 5- of 2-, potassium carbonate is according to molar ratio 1:(1-3): (2-4) It feeds intake, and according to the intermediate B1: toluene: ethyl alcohol: water is that toluene, second is added in 1mmol:1-10mL:1-10mL:1-10mL Alcohol and water, under nitrogen protection, according to the intermediate B1Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, It is warming up to 60-100 DEG C, reacts 4-30h, is restored to room temperature, according to the intermediate B1Substance meter, be added 1-3 times The intermediate B2, it is warming up to 60-100 DEG C of reaction 6-30h, after the reaction was completed, processing obtains target compound C.
The third aspect of the invention provides a kind of organic illuminating element, comprising: anode, cathode and photosphere out, it is described Out the material of photosphere include such as the above-mentioned bipolarity compound based on 1,3,4- thiadiazoles, and it is described go out photosphere be laminated in institute It states on cathode, the cathode is laminated on the anode.
As a kind of perferred technical scheme, organic illuminating element further includes luminescent layer, and the luminescent layer is folded in described Between anode and the cathode, the material of the luminescent layer includes such as the above-mentioned bipolarity chemical combination based on 1,3,4- thiadiazoles Object.
The present invention with it is very strong draw electronic capability 1,3,4- thiadiazoles be core group, its 2,5 respectively with Arlydene is π bridge, and connection has electronics confession/acceptor ability group, and being formed a kind of novel has ambipolar compound. The electronic capability of haling of the mother nucleus structure symmetry of 1,3,4- thiadiazoles presents the compound structure extended through π bridge The close-packed structure of sequence, the introducing with ambipolar benzheterocycle further increase the rigid of compound entirety structure Property and steric hindrance it is big, such compound as go out photosphere add to except electrode, it can be achieved that light near the cathode caused by low light Loss is learned, light extraction efficiency is improved, is that one kind preferably goes out photosphere material.Further, since compound has the mother for haling electronics Nuclear structure and confession/acceptor groups, make it have stronger charge balance ability, and the conjugacy that π bridge interrupts is effectively improved electron The problem of being reduced in a molecule by band gap caused by the charge of intramolecular with electron-withdrawing group, as luminous layer main body When material is applied to organic electroluminescence device, the higher triplet of such compound and wider band gap can be effective Prevent the backward energy from object to main body from transmitting, the charge transport ability of balance has ensured that carrier is being sent out to a greater extent The compound transition of photosphere assigns device with the landing of lower driving voltage, higher device efficiency and lesser efficiency, is also A kind of excellent luminescent layer material of main part.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the present invention has the organic electroluminescence device of photosphere structure out；
Fig. 2 is wavelength-light intensity characteristics curve graph of device 4, device 14 and device 26；
Fig. 3 is the voltage-current density-luminosity response figure of device 4, device 14 and device 26；
Fig. 4 is current density-current efficiency-power efficiency characteristic curve graph of device 4, device 14 and device 26；
Fig. 5 is brightness-external quantum efficiency characteristic curve graph of device 4, device 14 and device 26.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.According to the technical essence of the invention to following embodiment Made any simple modification, equivalent variations etc., still fall within the protection scope of technical solution of the present invention.The present invention is not limited to Under content as described in the examples.
Embodiment 1: compound (1) can be synthesized by following method:
(1) synthesis of intermediate a:
In 500mL there-necked flask, be added the bromo- 1H- benzimidazole (39.41g, 200mmol) of 2-, iodobenzene (40.79g, 200mmol), crown ether (5.29g, 20mmol), potassium carbonate (82.92g, 600mmol), dimethyl acetamide (200g), nitrogen are protected Under shield, cuprous iodide (3.81g, 20mmol) is continuously added, is warming up to 165 DEG C, reacts 12h, HPLC monitoring reaction is completed, drop Temperature stops reaction.Washing, filtering, ethyl alcohol are beaten one time, and intermediate a can be obtained0: the bromo- 1- phenyl -1H- benzimidazole of 2- 47.52g yield 87%.
In 1L there-necked flask, intermediate a is added0(40.97g, 150mmol), 4- bromobenzeneboronic acid (30.12g, 150mmol), potassium carbonate (41.46g, 300mmol), toluene (300mL), ethyl alcohol (150mL), water (150mL), nitrogen protection Under, tetrakis triphenylphosphine palladium (0.35g, 0.3mmol) is continuously added, is warming up to 85 DEG C, reacts 10h, HPLC monitoring has been reacted At cooling stops reaction.Washing, filtering, mother liquor concentrations, merge filter residue and concentrated mother liquor can be obtained with pillar layer separation Intermediate a:2- (4- bromophenyl) -1- phenyl -1H- benzimidazole 44.00g, yield 84%.
(2) synthesis of intermediate b:
In 1L there-necked flask, intermediate a (34.92g, 100mmol), tetrahydrofuran (350mL) is added, under nitrogen protection, - 78 DEG C of stirring 0.5h are cooled to, react 1h with the n-BuLi cyclohexane solution 50mL that dropping funel is slowly added to 2mol/L Afterwards, it is subsequently added into triethyl borate (14.60g, 100mmol) the reaction was continued 2h, is warmed to room temperature reaction 10h, HPLC monitoring reaction It completes, after being cooled to 0 DEG C, reaction is hydrolyzed in the hydrochloric acid that 100mL 2mol/L is added, and stands liquid separation, aqueous layer with ethyl acetate Twice of extraction merges organic layer concentration, intermediate b:(4- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) phenyl can be obtained) boron Sour 25.13g, yield 80%.
(3) synthesis of target compound c:
In 500mL there-necked flask, intermediate b (21.99g, 70mmol), the bromo- 5- of 2- chloro- 1,3,4- thiadiazoles are added (6.98g, 35mmol), potassium carbonate (19.35g, 140mmol), toluene (150mL), ethyl alcohol (70mL), water (70mL), nitrogen are protected Under shield, tetrakis triphenylphosphine palladium (0.16g, 0.14mmol) is continuously added, is warming up to 85 DEG C, reacts 14h, HPLC monitoring reaction It completes, cooling stops reaction.Washing, filtering, mother liquor concentrations, merging filter residue and concentrated mother liquor can be obtained with pillar layer separation To target compound c: compound (1) 19.18g, yield 88%.
Mass spectrograph MALDI-TOF-MS (m/z)=622.7496, theoretical molecular weight: 622.7500； Anal.Calcd for C40H26N6(%): C 77.15, H 4.21, N 13.50 Found:C 77.15, H 4.20, N 13.50.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (1).
Embodiment 2: compound (20) can be synthesized by following method:
(1) intermediate a1、a2Synthesis:
By the iodobenzene (40.79g, 200mmol) in embodiment 1 (1) replace with 2- iodine dibenzofurans (58.82g, 200mmol), other synthesis processes are the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained10: the bromo- 1- (two of 2- Benzofuran -2- base) -1H- benzimidazole 60.29g, yield 83%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment10(54.48g, 150mmol), intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes1: 2- (4- bromobenzene Base) -1- (dibenzofurans -2- base) -1H- benzimidazole 52.72g, yield 80%；
By the iodobenzene (40.79g, 200mmol) in embodiment 1 (1) replace with the iodo- 1,1'- biphenyl of 3- (56.02g, 200mmol), other synthesis processes are the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained20: 1- ([1,1'- Biphenyl] -3- base) the bromo- 1H- benzimidazole 59.37g of -2-, yield 85%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment20(52.38g, 150mmol), intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes2: 2- (4- bromobenzene Base) -1- (dibenzofurans -2- base) -1H- benzimidazole 53.59g, yield 84%.
(2) intermediate b1、b2Synthesis:
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment1(43.93g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes1: (4- (1- (hexichol And furans -2- base) -1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 32.34g, yield 80%.
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment2(42.53g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes2: (4- (1- ([1, 1'- biphenyl] -3- base) -1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 31.22g, yield 80%.
(3) synthesis of target compound c:
In 500mL there-necked flask, intermediate b is added1The chloro- 1,3,4- thiadiazoles of (14.15g, 35mmol), the bromo- 5- of 2- (6.98g, 35mmol), potassium carbonate (19.35g, 140mmol), toluene (150mL), ethyl alcohol (70mL), water (70mL), nitrogen are protected Under shield, tetrakis triphenylphosphine palladium (0.16g, 0.14mmol) is continuously added, is warming up to 85 DEG C, reacts 7h, HPLC monitoring has been reacted At intermediate b is added in recovery to room temperature2(13.66g, 35mmol), the reaction was continued 10h, HPLC monitoring reaction completion, cooling Stop reaction.Washing, filtering, mother liquor concentrations, merging filter residue and concentrated mother liquor with pillar layer separation can be obtained target chemical combination Object c: compound (20) 19.88g, yield 72%.
Mass spectrograph MALDI-TOF-MS (m/z)=788.9296, theoretical molecular weight: 788.9290； Anal.Calcd for C52H32N6(%): C 79.17, H 4.09, N 10.65 Found:C 79.18, H 4.10, N 10.65.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (20).
Embodiment 3: compound (35) can be synthesized by following method:
(1) intermediate a0Synthesis:
Iodobenzene (40.79g, 200mmol) in embodiment 1 (1) is replaced with into 2- iodine naphthalene (50.81g, 200mmol), His synthesis process is the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained0: the bromo- 1- of 2- (naphthalene -2- base) -1H- benzene And imidazoles 54.30g, yield 84%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment0(48.48g, 150mmol), intermediate a:2- (4- bromobenzene can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes Base) -1- (naphthalene -2- base) -1H- benzimidazole 49.11g, yield 82%；(2) synthesis of intermediate b:
By a (34.92g, 100mmol) in embodiment 1 (2) replace in the present embodiment a (39.93g, 100mmol), intermediate b:(4- (1- (naphthalene -2- can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes Base) -1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 29.50g, yield 81%.
(3) synthesis of intermediate c:
B (21.99g, 70mmol) in embodiment 1 (3) is replaced with into the b (25.49g, 70mmol) in the present embodiment, Target compound c: compound (35) can be obtained with the synthesis process of 1 target compound c of embodiment in other synthesis processes 21.51g yield 85%.
Mass spectrograph MALDI-TOF-MS (m/z)=722.8695, theoretical molecular weight: 722.8700； Anal.Calcd for C48H30N6(%): C 79.76, H 4.18, N 11.63Found:C 79.75, H 4.20, N 11.62.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (35).
Embodiment 4: compound (69) can be synthesized by following method:
(1) intermediate a1、a2Synthesis:
Iodobenzene (40.79g, 200mmol) in embodiment 1 (1) is replaced with into the iodo- 9,9- dimethyl -9H- fluorenes of 4- (63.83g, 200mmol), other synthesis processes are the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained10: 2- Bromo- 1- (9,9- dimethyl -9H- fluorenes -4- base) -1H- benzimidazole 63.84g, yield 82%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment10(58.39g, 150mmol), 4- bromobenzeneboronic acid (30.12g, 150mmol) replaces with 3- bromobenzeneboronic acid (30.12g, 150mmol), other synthesis Intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in process1: 2- (3- bromophenyl) -1- (9,9- dimethyl - 9H- fluorenes -4- base) -1H- benzimidazole 54.45g, yield 78%；
By the 4- bromobenzeneboronic acid (30.12g, 150mmol) in embodiment 1 (1) replace with 3- bromobenzeneboronic acid (30.12g, 150mmol), intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes2: 2- (3- bromobenzene Base) -1- phenyl -1H- benzimidazole 44.00g, yield 84%.
(2) intermediate b1、b2Synthesis:
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment1(46.54g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes1: (3- (1- (9,9- Dimethyl -9H- fluorenes -4- base) -1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 33.99g, yield 79%.
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment2(34.92g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes2: (3- (1- phenyl- 1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 25.44g, yield 81%.
(3) synthesis of target compound c:
By the b in embodiment 2 (3)1(14.15g, 35mmol) replaces with the b in the present embodiment1(15.06g, 35mmol), By the b in embodiment 2 (3)2(13.66g, 35mmol) replaces with the b in the present embodiment2(11.00g, 35mmol), other synthesis Target compound c: compound (69) 19.40g, yield can be obtained with the synthesis process of 2 target compound c of embodiment in process 75%.
Mass spectrograph MALDI-TOF-MS (m/z)=738.9136, theoretical molecular weight: 738.9130； Anal.Calcd for C49H34N6(%): C 79.65, H 4.64, N 11.37Found:C 79.65, H 4.65, N 11.35.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (69).
Embodiment 5: compound (96) can be synthesized by following method:
(1) intermediate a1、a2Synthesis:
By the 4- bromobenzeneboronic acid (30.12g, 150mmol) in embodiment 1 (1) replace with 3- bromobenzeneboronic acid (30.12g, 150mmol), intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes1: 2- (3- bromobenzene Base) -1- phenyl -1H- benzimidazole 44.00g, yield 84%.
Iodobenzene (40.79g, 200mmol) in embodiment 1 (1) is replaced with into the iodo- 9- phenyl -9H- carbazole of 3- (73.84g, 200mmol), other synthesis processes are the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained20: 3- (the bromo- 1H- benzimidazole -1- base of 2-) -9- phenyl -9H- carbazole 70.13g, yield 80%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment20(65.75g, 150mmol), 4- bromobenzeneboronic acid (30.12g, 150mmol) replaces with 3- bromobenzeneboronic acid (30.12g, 150mmol), other synthesis Intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in process2: 3- (2- (3- bromophenyl) -1H- benzimidazole - 1- yl) -9- phenyl -9H- carbazole 59.42g, yield 77%；
(2) intermediate b1、b2Synthesis:
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment1(34.92g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes1: (3- (1- phenyl- 1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 25.44g, yield 81%.
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment2(51.44g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes2: (3- (1- (9- benzene Base -9H- carbazole -3- base) -1H- benzimidazolyl-2 radicals-yl) phenyl) boric acid 38.34g, yield 80%.
(3) synthesis of target compound c:
By the b in embodiment 2 (3)1(14.15g, 35mmol) replaces with the b in the present embodiment1(11.00g, 35mmol), By the b in embodiment 2 (3)2(13.66g, 35mmol) replaces with the b in the present embodiment2(16.78g, 35mmol), other synthesis Target compound c: compound (96) 20.40g, yield can be obtained with the synthesis process of 2 target compound c of embodiment in process 74%.
Mass spectrograph MALDI-TOF-MS (m/z)=787.9443, theoretical molecular weight: 787.9450；Anal.Calcd for C52H33N7(%): C 79.27, H 4.22, N 12.44Found:C 79.25, H 4.22, N 12.45.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (96).
Embodiment 6: compound (121) can be synthesized by following method:
(1) synthesis of intermediate a:
4- bromobenzeneboronic acid (30.12g, 150mmol) in embodiment 1 (1) is replaced with into (3'- bromo- [1,1'- biphenyl]- 3- yl) boric acid (41.54g, 150mmol), other synthesis processes can be obtained with the synthesis process of 1 intermediate a of embodiment Mesosome a:2- (bromo- [1,1'- the biphenyl] -3- base of 3'-) -1- phenyl -1H- benzimidazole 54.23g, yield 85%；
(2) synthesis of intermediate b:
By a (34.92g, 100mmol) in embodiment 1 (2) replace in the present embodiment a (42.53g, 100mmol), other synthesis processes are with the synthesis process of 1 intermediate b of embodiment, can be obtained intermediate b:2- (3'- it is bromo- [1, 1'- biphenyl] -3- base) -1- phenyl -1H- benzimidazole 34.87g, yield 82%.
(3) synthesis of intermediate c:
B (21.99g, 70mmol) in embodiment 1 (3) is replaced with into the b (29.77g, 70mmol) in the present embodiment, Target compound c: compound (121) can be obtained with the synthesis process of 1 target compound c of embodiment in other synthesis processes 23.60g yield 87%.
Mass spectrograph MALDI-TOF-MS (m/z)=774.9463, theoretical molecular weight: 774.9460； Anal.Calcd for C52H34N6(%): C 80.60, H 4.42, N 10.84Found:C, 80.60, H 4.40, N 10.85.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (121).
Embodiment 7: compound (150) can be synthesized by following method:
(1) intermediate a1、a2Synthesis:
Iodobenzene (40.79g, 200mmol) in embodiment 1 (1) is replaced with into 1- iodine naphthalene (50.81g, 200mmol), His synthesis process is the same as 1 intermediate a of embodiment0Synthesis process, intermediate a can be obtained10: the bromo- 1- of 2- (naphthalene -1- base) -1H- Benzimidazole 50.42g, yield 78%；
By a in embodiment 1 (1)0(40.97g, 150mmol) replaces with a in the present embodiment10(48.48g, 150mmol), 4- bromobenzeneboronic acid (30.12g, 150mmol) replaces with (5- bromonaphthalene -1- base) boric acid (37.63g, 150mmol), Intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in other synthesis processes1: 2- (5- bromonaphthalene -1- base) -1- (naphthalene -1- base) -1H- benzimidazole 50.55g, yield 75%；
4- bromobenzeneboronic acid (30.12g, 150mmol) in embodiment 1 (1) is replaced with into (5- bromonaphthalene -1- base) boric acid Intermediate a can be obtained with the synthesis process of 1 intermediate a of embodiment in (37.63g, 150mmol), other synthesis processes2: 2- (5- bromonaphthalene -1- base) -1- phenyl -1H- benzimidazole 46.12g, yield 77%.
(2) intermediate b1、b2Synthesis:
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment1(44.94g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes1: (5- (1- (naphthalene- 1- yl) -1H- benzimidazolyl-2 radicals-yl) naphthalene -1- base) boric acid 32.73g, yield 79%.
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment2(39.93g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes2: (5- (1- phenyl- 1H- benzimidazolyl-2 radicals-yl) naphthalene -1- base) phenyl boric acid 28.77g, yield 79%.
(3) synthesis of target compound c:
By the b in embodiment 2 (3)1(14.15g, 35mmol) replaces with the b in the present embodiment1(14.50g, 35mmol), By the b in embodiment 2 (3)2(13.66g, 35mmol) replaces with the b in the present embodiment2(12.75g, 35mmol), other synthesis Process can be obtained target compound c: compound (150) 18.94g with the synthesis process of 2 target compound c of embodiment, receive Rate 70%.
Mass spectrograph MALDI-TOF-MS (m/z)=772.9304, theoretical molecular weight: 772.9300； Anal.Calcd for C52H32N6(%): C 80.81, H 4.17, N 10.87Found:C 80.80, H 4.19, N 10.85.By mass spectrometric data and member Element analysis result is it is found that the product structure is correct, for compound (150).
Embodiment 8: compound (164) can be synthesized by following method:
(1) intermediate a1、a2Synthesis:
In 1L there-necked flask, 2- bromo benzothiazole (32.11g, 150mmol), (6- bromonaphthalene -1- base) boric acid is added (37.63g, 150mmol), potassium carbonate (41.46g, 300mmol), tetrahydrofuran (400mL), water (150mL), nitrogen protection Under, tetrakis triphenylphosphine palladium (0.35g, 0.3mmol) is continuously added, is warming up to 85 DEG C, reacts 10h, HPLC monitoring has been reacted At cooling stops reaction.Washing, filtering, mother liquor concentrations, merge filter residue and concentrated mother liquor can be obtained with pillar layer separation Intermediate a1: 2- (6- bromonaphthalene -1- base) benzothiazole 38.28g, yield 75%；
Intermediate a2Synthesis process with intermediate a1Synthesis process, only by (6- bromonaphthalene -1- base) boric acid (37.63g, 150mmol) replaces with (5- bromonaphthalene -2- base) boric acid (37.63g, 150mmol), and intermediate a can be obtained2: 2- (5- bromonaphthalene -2- base) benzothiazole 39.30g, yield 77%.
(2) intermediate b1、b2Synthesis:
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment1(34.02g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes1: (5- (benzo thiophene Azoles -2- base) naphthalene -2- base) boric acid 24.72g, yield 81%.
A (34.92g, 100mmol) in embodiment 1 (2) is replaced with into a in the present embodiment2(34.02g, 100mmol), intermediate b can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes2: (6- (benzo thiophene Azoles -2- base) naphthalene -1- base) boric acid 24.11g, yield 79%.
(3) synthesis of target compound c:
By the b in embodiment 2 (3)1(14.15g, 35mmol) replaces with the b in the present embodiment1(10.68g, 35mmol), By the b in embodiment 2 (3)2(13.66g, 35mmol) replaces with the b in the present embodiment2(10.68g, 35mmol), other synthesis Process can be obtained target compound c: compound (164) 15.24g with the synthesis process of 2 target compound c of embodiment, receive Rate 72%.
Mass spectrograph MALDI-TOF-MS (m/z)=604.7634, theoretical molecular weight: 604.7640； Anal.Calcd for C36H20N4(%): C 71.50, H 3.33, N 9.26Found:C 71.50, H 3.35, N 9.25.By mass spectrometric data and element Result is analyzed it is found that the product structure is correct, for compound (164).
Embodiment 9: compound (173) can be synthesized by following method:
2- bromo benzothiazole (32.11g, 150mmol) in embodiment 8 (1) is replaced with into 1,1- dioxo -2- bromobenzene And thiazole (36.91g, 150mmol), (6- bromonaphthalene -1- base) boric acid (37.63g, 150mmol) replace with (3'- bromo- [1,1'- Phenyl] -4- base) boric acid (41.54g, 150mmol), synthesis process of other synthesis processes with 8 intermediate a of embodiment Obtain intermediate a:1,1- dioxo -2- (bromo- [1,1'- the biphenyl] -4- base of 3'-) benzothiazole 50.78g, yield 85%.
(2) synthesis of intermediate b:
By a (34.92g, 100mmol) in embodiment 1 (2) replace in the present embodiment a (39.83g, 100mmol), intermediate b:(4'- (1,1- bis- can be obtained with the synthesis process of 1 intermediate b of embodiment in other synthesis processes Oxo-benzothiazole -2- base)-[1,1'- biphenyl] -3- base) boric acid 29.78g, yield 82%.
(3) synthesis of target compound c:
B (21.99g, 70mmol) in embodiment 1 (3) is replaced with into the b (25.42g, 70mmol) in the present embodiment, Target compound c: compound (173) can be obtained with the synthesis process of 1 target compound c of embodiment in other synthesis processes 21.95g yield 87%.
Mass spectrograph MALDI-TOF-MS (m/z)=720.8364, theoretical molecular weight: 720.8360； Anal.Calcd for C40H24N4(%): C 66.65, H 3.36, N 7.77Found:C 66.65, H 3.35, N 7.78.By mass spectrometric data and element Result is analyzed it is found that the product structure is correct, for compound (173).
Embodiment 10: compound (190) can be synthesized by following method:
(1) synthesis of intermediate a:
2- bromo benzothiazole (32.11g, 150mmol) in embodiment 8 (1) is replaced with into 2- bromine benzoxazoles (29.70g, 150mmol), (6- bromonaphthalene -1- base) boric acid (37.63g, 150mmol) replace with (7- bromonaphthalene -1- base) boric acid Intermediate a:2- can be obtained with the synthesis process of 8 intermediate a of embodiment in (37.63g, 150mmol), other synthesis processes (6- bromonaphthalene -1- base) benzoxazoles 37.44g, yield 77%.
(2) synthesis of intermediate b:
By a (34.92g, 100mmol) in embodiment 1 (2) replace in the present embodiment a (32.42g, 100mmol), other synthesis processes are with the synthesis process of 1 intermediate b of embodiment, and intermediate b:(5- can be obtained, and (benzo is disliked Azoles -2- base) naphthalene -2- base) boric acid 23.42g, yield 81%.
(3) synthesis of target compound c:
B (21.99g, 70mmol) in embodiment 1 (3) is replaced with into the b (20.24g, 70mmol) in the present embodiment, Target compound c: compound (190) can be obtained with the synthesis process of 1 target compound c of embodiment in other synthesis processes 14.83g yield 74%.
Mass spectrograph MALDI-TOF-MS (m/z)=572.6417, theoretical molecular weight: 572.6420； Anal.Calcd for C36H20N4(%): C 75.51, H 3.52, N 9.78Found:C 75.50, H 3.52, N 9.80.By mass spectrometric data and element Result is analyzed it is found that the product structure is correct, for compound (190).
According to above compound sample preparation method as described in the examples, the system to compound 1-193 can be completed It is standby.
Application Example 1
It is provided by the present invention to be carried out as luminescent layer material of main part based on the bipolarity compound of 1,3,4- thiadiazoles Device preparation can be prepared according to this method.
By film thickness be 150nm ITO (tin indium oxide) glass substrate in succession in cleaning agent and deionized water with ultrasonic wave 1h is cleaned, successively continues ultrasonic cleaning 30 minutes with acetone and isopropanol later, is then dried in vacuo 2 hours (105 DEG C), The UV ozone treatment for carrying out 15 minutes afterwards, is sent to vacuum evaporation plating machine for ito glass substrate.In ITO in a manner of covering anode The MoO for the following structural formula that one tunic thickness of upper vapor deposition is 60nm3(molybdenum trioxide) forms hole injection layer.Then, with covering The mode of hole injection layer, NPB (N, N'- diphenyl-N, N'- (the 1- naphthalene for the following structural formula that one tunic thickness of vapor deposition is 60nm Base) -1,1'- biphenyl -4,4'- diamines) form hole transmission layer.Over the hole-transporting layer, one tunic thickness of vapor deposition is 20nm's It adulterates Ir (ppy)3The bipolarity compound provided by the invention of (three (2- phenylpyridines) close iridium) forms luminescent layer, with quality Score meter, Ir (ppy)3: bipolarity compound provided by the invention is 5:95.Secondly, being sent out in a manner of covering luminescent layer Be deposited on photosphere a tunic thickness be 30nm following structural formula TmPyPB (3,3'- [5'- [3- (3- pyridyl group) phenyl] [1, 1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines) form electron transfer layer.Finally, being successively deposited on the electron transport layer The Al (aluminium) of the LiF (lithium fluoride) and 100nm of 1nm form electron injecting layer and cathode.Specific structure are as follows: ITO/ MoO3 (10nm)/NPB (60nm)/bipolarity provided by the invention compound: 5%wt Ir (ppy)3 (20nm)/TmPyPB(30nm)/ LiF(1nm)/Al(100nm)。
Application Example 2
As the luminescent layer material of main part and out light provided by the present invention based on the bipolarity compound of 1,3,4- thiadiazoles The device preparation that layer material carries out can be prepared according to this method.
By ito glass substrate that film thickness is 150nm in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, it Successively continue ultrasonic cleaning 30 minutes with acetone and isopropanol afterwards, then 2 hours (105 DEG C) of vacuum drying, followed by 15 points The UV ozone treatment of clock, is sent to vacuum evaporation plating machine for ito glass substrate.One layer is deposited on ITO in a manner of covering anode Film thickness is the MoO of the following structural formula of 10nm3Form hole injection layer.Then, it in a manner of covering hole injection layer, steams It plates the NPB that a tunic thickness is 60nm and forms hole transmission layer.Over the hole-transporting layer, one tunic thickness of vapor deposition is mixing for 20nm Miscellaneous Ir (ppy)3The bipolarity compound provided by the invention of (three (2- phenylpyridines) close iridium) forms luminescent layer, with quality point Number meter, Ir (ppy)3: bipolarity compound provided by the invention is 5:95.Secondly, being shone in a manner of covering luminescent layer The TmPyPB that a tunic thickness is 30nm is deposited on layer and forms electron transfer layer.Then, 1nm is successively deposited on the electron transport layer LiF and the Al of 100nm form electron injecting layer and cathode.Finally, one layer is deposited on cathode in a manner of covered cathode Film thickness is that the bipolarity compound provided by the invention of 10nm forms out photosphere.Specific structure are as follows: ITO/ MoO3(10nm)/ NPB (60nm)/bipolarity provided by the invention compound: 5%wt Ir (ppy)3 (20nm)/TmPyPB(30nm)/LiF (1nm)/Al (100nm)/bipolarity provided by the invention compound (10nm).
Application Example 3
Device provided by the present invention based on the bipolarity compound of 1,3,4- thiadiazoles as photosphere material progress out Preparation can be prepared according to this method.
By ito glass substrate that film thickness is 150nm in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, it Successively continue ultrasonic cleaning 30 minutes with acetone and isopropanol afterwards, then 2 hours (105 DEG C) of vacuum drying, followed by 15 points The UV ozone treatment of clock, is sent to vacuum evaporation plating machine for ito glass substrate.One layer is deposited on ITO in a manner of covering anode Film thickness is the MoO of the following structural formula of 10nm3Form hole injection layer.Then, it in a manner of covering hole injection layer, steams It plates the NPB that a tunic thickness is 60nm and forms hole transmission layer.Over the hole-transporting layer, one tunic thickness of vapor deposition is mixing for 20nm Miscellaneous Ir (ppy)3Have following structure formula CBP (4,4'- bis- (9- carbazole) biphenyl) formed luminescent layer, based on mass fraction, Ir(ppy)3: CBP 5:95.Secondly, it is 30nm's that a tunic thickness is deposited on the light-emitting layer in a manner of covering luminescent layer TmPyPB forms electron transfer layer.Then, the Al that the LiF and 100nm of 1nm are successively deposited on the electron transport layer forms electronics Implanted layer and cathode.Finally, it is the provided by the invention of 10nm that a tunic thickness is deposited on cathode in a manner of covered cathode Bipolarity compound forms out photosphere.Specific structure are as follows: ITO/MoO3(10nm)/NPB (60nm)/CBP:5%wt Ir (ppy)3 (20nm)/TmPyPB (30nm)/LiF (1nm)/Al (100nm)/bipolarity provided by the invention compound (10nm).
Comparative example
By ito glass substrate that film thickness is 150nm in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, it Successively continue ultrasonic cleaning 30 minutes with acetone and isopropanol afterwards, then 2 hours (105 DEG C) of vacuum drying, followed by 15 points The UV ozone treatment of clock, is sent to vacuum evaporation plating machine for ito glass substrate.One layer is deposited on ITO in a manner of covering anode Film thickness is the MoO of the following structural formula of 10nm3Form hole injection layer.Then, it in a manner of covering hole injection layer, steams It plates the NPB that a tunic thickness is 60nm and forms hole transmission layer.Over the hole-transporting layer, one tunic thickness of vapor deposition is mixing for 20nm Miscellaneous Ir (ppy)3The CBP (4,4'- bis- (9- carbazole) biphenyl) of (three (2- phenylpyridines) close iridium) forms luminescent layer, with quality point Number meter, Ir (ppy)3: CBP 5:95.Secondly, it is 30nm that a tunic thickness is deposited on the light-emitting layer in a manner of covering luminescent layer TmPyPB formed electron transfer layer.Then, the Al that the LiF and 100nm of 1nm are successively deposited on the electron transport layer forms electricity Sub- implanted layer and cathode.Finally, a tunic thickness is deposited on cathode and is provided for the present invention of 10nm in a manner of covered cathode Bipolarity compound form out photosphere.Specific structure are as follows: ITO/MoO3(10nm)/NPB (60nm)/CBP:5%wt Ir (ppy)3(20nm)/TmPyPB(30nm)/LiF(1nm)/Al(100nm)。
The survey of characteristics of luminescence when by the organic electroluminescence device made according to embodiment of above application DC voltage It is shown in table 1 to determine result summary:
1 organic electroluminescence device performance characterization of table
It can be seen from table it is provided by the present invention be based on 1,3,4- thiadiazoles bipolarity compound as go out light Layer material is remarkably improved the light extraction efficiency of device, luminous intensity, current efficiency, power efficiency and the outer quantum effect of device Performance in terms of rate is obviously improved, and is a kind of ideal photosphere material out.In addition, provided by the present invention be based on 1, The bipolarity compound of 3,4- thiadiazoles also has excellent performance using upper luminescent layer material of main part, can effectively realize bright On bright uniform green light, start voltage, light emission luminance, current efficiency, power efficiency, in terms of improve The comprehensive performance of device.
It should be noted that wavelength as shown in Figure 2-light intensity characteristics curve graph, provided by the invention to be based on 1,3,4- The bipolarity compound of thiadiazoles is independent as the device 4 of luminescent layer material of main part preparation and as luminous layer main body material Device 14 prepared by material and out photosphere material has issued the green light of pure saturation.As shown in Figure 3 and Figure 4, base provided by the invention In the independent device 4 and existing with CBP as the preparation of luminescent layer material of main part of the bipolarity compound of 1,3,4- thiadiazoles Device 20 as the preparation of luminescent layer material of main part is compared, the charge transport ability of balance and efficient Carrier recombination transition So that device brightness reaches 59040cd/m2, current efficiency and power efficiency respectively reach 128.62cd/A and 111.94lm/ W improves the comprehensive performance of device, as photosphere material out preparation device 14 with it is not set go out photosphere device 4 compared with, Light extraction efficiency is obviously improved, and device brightness reaches 67750cd/m2, current efficiency reaches 153.45cd/A, and power efficiency reaches To 145.32lm/W, efficiently solve the problems, such as light in the internal dissipation of device.Brightness-external quantum efficiency characteristic as shown in Figure 5 Curve graph, the bipolarity compound provided by the invention for being based on 1,3,4- thiadiazoles is independent to be used as luminescent layer material of main part system Compared with the existing device 20 prepared using CBP as luminescent layer material of main part, the external quantum efficiency of device obtains standby device 4 Improvement to a certain extent is used as photosphere when the bipolarity compound provided by the invention for being based on 1,3,4- thiadiazoles is added When structure prepares device 14, light extraction efficiency, which has, significantly to be promoted, and external quantum efficiency can promote 30% or more, is greatly changed It has been apt to the drop rolling problem of device.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (9)

1. being based on the bipolarity compound of 1,3,4- thiadiazoles, which is characterized in that shown in general structure following (I):
Wherein, Ar1、Ar2Independently are as follows: any one of the arlydene that substituted or unsubstituted carbon number is 6 to 24, Ar1、 Ar2It is identical or different；
R1、R2、R3、R4、R5、R6、R7、R8Independently are as follows: alkoxy that alkyl that hydrogen, carbon number are 1 to 4, carbon number are 1 to 4, Aryl that aryloxy group that substituted or unsubstituted carbon number is 6 to 12, substituted or unsubstituted carbon number are 6 to 12 replaces or does not take Any one of the heterocycle that the carbon number in generation is 5 to 12, R1、R2、R3、R4、R5、R6、R7、R8It is identical or different；
X1、X2Independently are as follows: S, O=S=O, O or N-L；
Wherein, the L is selected from: aryl that substituted or unsubstituted carbon number is 6 to 24, substituted or unsubstituted carbon number are 6 to 24 Aromatic heterocyclic, substituted or unsubstituted carbon number be 12 to 24 fluorenyl, substituted or unsubstituted carbon number be 6 to 24 aryl amine Any one of, X1、X2It is identical or different.
2. the bipolarity compound according to claim 1 for being based on 1,3,4- thiadiazoles, which is characterized in that as the Ar1、 Ar2Independently are as follows: substituted carbon number be 6 to 24 arlydene in it is any when, the substituent group of the arlydene is selected from: Alkyl that carbon number is 1 to 4, carbon number are any one of 6 to 10 aryl；
As the R1、R2、R3、R4、R5、R6、R7、R8Independently are as follows: aryloxy group, substituted carbon of the substituted carbon number for 6 to 12 When any in the heterocycle that aryl that number is 6 to 12, substituted carbon number are 5 to 12, the aryloxy group, the aryl and institute The substituent group for stating heterocycle is independently selected from: alkyl that carbon number is 1 to 4, carbon number are any one of 6 to 10 aryl；
When the L is selected from: aryl that substituted carbon number is 6 to 24, the aromatic heterocyclic that substituted carbon number is 6 to 24, substituted carbon When any in the aryl amine that fluorenyl that number is 12 to 24, substituted carbon number are 6 to 24, the aryl, the aromatic heterocyclic, The substituent group of the fluorenyl and the aryl amine is independently selected from: the aryl that alkyl that carbon number is 1 to 4, carbon number are 6 to 10 Any one of.
3. the bipolarity compound according to claim 1 for being based on 1,3,4- thiadiazoles, which is characterized in that the R1、R2、 R3、R4、R5、R6、R7、R8It is hydrogen, then the general structure of the bipolarity compound is shown in following (II):
4. the bipolarity compound according to claim 1 for being based on 1,3,4- thiadiazoles, which is characterized in that the Ar1、Ar2 It is independently selected from: the Asia of aryl substitution that is alkyl-substituted or being 6 to 10 by carbon number that is unsubstituted, being 1 to 4 by carbon number Any one of phenyl, the Asia of aryl substitution that is alkyl-substituted or being 6 to 10 by carbon number that is unsubstituted, being 1 to 4 by carbon number Any one of xenyl, alternatively, aryl that is alkyl-substituted or being 6 to 10 by carbon number that is unsubstituted, being 1 to 4 by carbon number Any one of substituted naphthylene.
5. the bipolarity compound according to claim 1 for being based on 1,3,4- thiadiazoles, which is characterized in that the X1、X2Point It Wei N-L, wherein the X1、X2Corresponding L is independently selected from: it is unsubstituted, by carbon number be 1 to 4 it is alkyl-substituted Or any one of the aryl that the carbon number that replaces of the aryl for by carbon number being 6 to 10 is 6 to 24, it is unsubstituted, be 1 to 4 by carbon number Aryl that is alkyl-substituted or being 6 to 10 by carbon number replace carbon number be 6 to 24 any one of aromatic heterocyclic, alternatively, Any one of the fluorenyl that the carbon number that aryl that is unsubstituted or being 6 to 10 by carbon number replaces is 12 to 24.
6. the bipolarity compound according to claim 5 for being based on 1,3,4- thiadiazoles, which is characterized in that the X1、X2Point Any one not independent in such as flowering structure:
7. a kind of preparation method of such as bipolarity compound as claimed in any one of claims 1 to 6 for being based on 1,3,4- thiadiazoles, It is characterised in that it includes following route:
Synthesis step are as follows:
S1, intermediate A10、Ar1The corresponding halogenated boronic acid derivatives replaced, potassium carbonate are according to molar ratio 1:(1-3): (2-4) is thrown Material, and according to the intermediate A10: toluene: ethyl alcohol: water is that toluene, second alcohol and water is added in 1mmol:1-4mL:1-4mL:1-4mL, Under nitrogen protection, according to the intermediate A10Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, be warming up to 60-100 DEG C, 6-30h is reacted, processing obtains intermediate A1；
Intermediate A20、Ar2The corresponding halogenated boronic acid derivatives replaced, potassium carbonate are according to molar ratio 1:(1-3): (2-4) feeds intake, and According to the intermediate A20: toluene: ethyl alcohol: water is that toluene, second alcohol and water is added in 1mmol:1-4mL:1-4mL:1-4mL, in nitrogen Under gas shielded, according to the intermediate A20Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, be warming up to 60- 100 DEG C, 6-30h is reacted, processing obtains intermediate A2；
S2, according to the intermediate A1: tetrahydrofuran is 1mmol:2-5mL by the intermediate A1It is dissolved in tetrahydrofuran, nitrogen Under gas shielded, -78 DEG C of stirring 0.3-2h are cooled to, by n-BuLi cyclohexane solution with itself and the intermediate A1Ratio is After 0.2-4mL:1mmol is added and reacts 0.5-3h, according to the intermediate A1Substance meter, 1-3 times of boric acid is added Triethyl the reaction was continued 1-4h is warmed to room temperature reaction 6-20h reaction and completes, after being cooled to 0 DEG C, according to the intermediate A1: salt Acid is that reaction is hydrolyzed in 1mmol:0.2-4mL addition hydrochloric acid solution, and processing obtains intermediate B1；
According to the intermediate A2: tetrahydrofuran is 1mmol:2-5mL by the intermediate A2It is dissolved in tetrahydrofuran, nitrogen Under protection, -78 DEG C of stirring 0.3-2h are cooled to, by n-BuLi cyclohexane solution with itself and the intermediate A2Ratio is 0.2- After 4mL:1mmol is added and reacts 0.5-3h, according to the intermediate A1Substance meter, 1-3 times of boron triethylenetetraminehexaacetic acid is added Ester the reaction was continued 1-4h is warmed to room temperature reaction 6-20h reaction and completes, after being cooled to 0 DEG C, according to the intermediate A1: hydrochloric acid is 1mmol:0.2-4mL is added hydrochloric acid solution and reaction is hydrolyzed, and processing obtains intermediate B1；
S3, the intermediate B1, the bromo- 5- of 2- chloro- 1,3,4- thiadiazoles, potassium carbonate are according to molar ratio 1:(1-3): (2-4) feeds intake, And according to the intermediate B1: toluene: ethyl alcohol: water is that toluene, second alcohol and water is added in 1mmol:1-10mL:1-10mL:1-10mL, Under nitrogen protection, according to the intermediate B1Substance meter, be added 1 ‰ -5% tetrakis triphenylphosphine palladium, be warming up to 60-100 DEG C, 4-30h is reacted, is restored to room temperature, according to the intermediate B1Substance meter, be added in 1-3 times described Mesosome B2, it is warming up to 60-100 DEG C of reaction 6-30h, after the reaction was completed, processing obtains target compound C.
8. a kind of organic illuminating element, comprising: anode, cathode and photosphere out, which is characterized in that it is described go out photosphere material include Such as bipolarity compound as claimed in any one of claims 1 to 6 for being based on 1,3,4- thiadiazoles, and the photosphere out is laminated in institute It states on cathode, the cathode is laminated on the anode.
9. a kind of organic illuminating element according to claim 8, which is characterized in that it further include luminescent layer, the luminescent layer It is folded between the anode and the cathode, the material of the luminescent layer includes such as base as claimed in any one of claims 1 to 6 In the bipolarity compound of 1,3,4- thiadiazoles.
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