CN109232474A - 1,2,4- thiadiazole compound and its preparation method and application - Google Patents

1,2,4- thiadiazole compound and its preparation method and application Download PDF

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CN109232474A
CN109232474A CN201811130417.4A CN201811130417A CN109232474A CN 109232474 A CN109232474 A CN 109232474A CN 201811130417 A CN201811130417 A CN 201811130417A CN 109232474 A CN109232474 A CN 109232474A
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CN109232474B (en
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穆广园
庄少卿
任春婷
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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Priority to JP2021517087A priority patent/JP2021524867A/en
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Abstract

The invention discloses 1,2,4- thiadiazole compounds and its preparation method and application.1,2, the 4- thiadiazole compound goes out photosphere material as OLED device, is remarkably improved the performance of luminous intensity, current efficiency, power efficiency, external quantum efficiency and coloration of device etc., and extend device lifetime.

Description

1,2,4- thiadiazole compound and its preparation method and application
Technical field
The present invention is to be related to field of photovoltaic materials, specifically, the present invention relates to 1,2, the 4- thiophenes as photosphere material out Diazoles compound and its preparation method and application.
Background technique
OLED, i.e. Organic Light Emitting Diode, also known as Organic Electricity laser display.OLED has self luminous characteristic, uses Very thin coating of organic material and glass substrate, when an electric current passes through it, organic material will shine, and OLED display screen Visible angle is big, and can save significantly on electric energy, therefore OLED is considered as one of the product of 21 century most future.But so far Until, OLED device is not able to achieve universalness application yet, wherein the efficiency of device is to restrict the major reason of its universalness.
Characterize an important parameter external quantum efficiency (η of OLED efficiencyEQE) following formula (1.1) indicates:
ηEQE=γ ηr·qeff·ηout (1.1)
Wherein γ represents carrier balance, ηrRepresent radiative excitons constant, qeffRepresent luminous quantum efficiency, ηoutRepresent light Coupling efficiency according to excellent functional layer material and optimizes the device of carrier balance, and carrier balance γ is believed that It is 1, radiative excitons constant ηrIt is 100%, in material qeffWhen promoting nearly 1, ηoutLargely limit luminous efficiency down.
So-called optical coupling output efficiency is exactly therefore ratio of the external mode in all mode improves optical coupling output Efficiency exactly minimizes influence of other mode to device in addition to external mode, improves the ratio of external mode as far as possible. ηoutIt is limited by total reflection caused by refractive index difference between organic material and substrate, so that light that organic layer issues and reflecting The phenomenon that light come interferes.
The major way for improving optical coupling output efficiency at present is to increase glass substrate roughness, coated microsphere grain, covering Lenticule, implantation low-refraction substance reduce optical waveguide effect, these methods improve light extraction efficiency, while but increasing device Preparation process.
In optical device, dielectric film can be deposited to reduce the reflection loss on surface on the surface of device, principle is thin The interference cancellation of film acts on, and light wave may further be construed to during propagation, due to the difference of boundary condition, at two kinds The distribution of the interface of different propagation mediums, energy is changed.Therefore, in the light emission side metal of organic electroluminescence device Light coupling layer material is introduced out except electrode, it will not impact the electric property of device substantially, only change light wave The distribution of transmission and reflected energy, enhances the output coupling ability of light.Go out light coupling layer material as microcavity OLED, mainly examines Consider their high refractive index index, the low absorptivity of visible-range interior focusing and be relatively easy to evaporation growth pattern etc. Characteristic enhances the coupling fan-out capability of light, improves device external quantum efficiency, reduces light in the loss of device inside.However, existing OLED go out photosphere material still have much room for improvement.
Summary of the invention
In one aspect of the invention, the present invention proposes a kind of compound.According to an embodiment of the invention, the chemical combination Object is structure shown in formula (I),
Wherein,
R1And R2It is separately hydrogen, cyano, nitro, amidino groups, sulfonyl, the sulfinat optionally replaced, optionally takes The C in generation1~20Alkyl, the amino optionally replaced, the amino optionally replaced, the C optionally replaced1~20Miscellaneous alkyl optionally replaces C1~20Silylation, the C optionally replaced6~30Aryl, the C optionally replaced3~30Heteroaryl, the C optionally replaced6~30Aryloxy group, optionally Substituted C6~30Arylthio, the C optionally replaced6~30Aryl amine or the C optionally replaced2~30Heterocycle；
L1And L2The separately C optionally to replace6~30Aryl or the C optionally replaced3~30Heteroaryl, d and e difference are only It is on the spot 0 or 1, and d and e are not 0 simultaneously.
Compound according to an embodiment of the present invention goes out photosphere material as OLED device, is remarkably improved the strong light of device The performance of degree, current efficiency, power efficiency, external quantum efficiency and coloration etc., and extend device lifetime.
In some embodiments of the invention, R1And R2At least one of be Wherein, Ar is the C optionally replaced6~50Aryl, the C optionally replaced3~50Heteroaryl optionally takes The C in generation6~50Aryloxy group, the C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine or the C optionally replaced2~50It is miscellaneous Ring group；A is the C optionally replaced1~20Alkyl, the amino optionally replaced, the C optionally replaced6~50Aryl, the C optionally replaced3~50It is miscellaneous Aryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine optionally takes The C in generation2~50Heterocycle；Each X is separately C, the N optionally replaced or each X is separately C, the N optionally replaced And the two adjacent X and C optionally replaced6~50Aryl, the C optionally replaced3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, The C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine and the C optionally replaced2~50At least one of heterocycle shape Cheng Binghuan；Y1And Y2It is separately C, N, O or S for optionally replacing, f is 0 or 1；A1And A2It is separately optionally substitution C1~20Miscellaneous alkyl, the C optionally replaced6~50Aryl, the amino optionally replaced, the C optionally replaced3~50Heteroaryl optionally replaces C6~50Aryloxy group, the C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine or the C optionally replaced2~50Heterocycle Base.
In some embodiments of the invention, R1And R2At least one of be following subformula:
Wherein, R3、R4、R5、R6、R7And R8The separately C optionally to replace1~20Alkyl, the ammonia optionally replaced Base, the C optionally replaced1~50Miscellaneous alkyl, the C optionally replaced1~20Silylation, the C optionally replaced6~50Aryl optionally replaces C3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine or The C optionally replaced2~50Heterocycle, X are foregoing, Y1And Y2Separately C, N, O or S optionally to replace；
A1And A2At least one of beWherein, Ar, A and X are foregoing.
In some embodiments of the invention, R1And R2At least one of be following subformula:
In some embodiments of the invention, the compound has the structure of one of:
According to an embodiment of the invention, the compound with the above structure, to have 1,2, the 4- thiophenes for haling electronic capability Diazole is parent nucleus, has ambipolar compound in its 3 and/or 5 upper one kind for introducing fused ring system formation.Conjugated degree The bonded thiadiazoles parent nucleus with vacant 3d track of higher fused ring system, conjugated degree is extended through S, so that compound Compactness in the solid state greatly improves, and improves the refractive index of compound, meanwhile, nonmetallic heavy atom S change to The track delocalization degree of body group effectively reduces light and sends out in device inside to improve the absorption of vibrations intensity of intramolecular The loss of light caused by raw total reflection, improve device current efficiency, power efficiency, external quantum efficiency and in terms of Performance.In addition, introducing heat-staple rigid radical with higher, carbazole group etc. on 1,2,4- thiadiazoles 3 and/or 5, The thermal stability for further having ensured overall molecule improves the service life of device.In general, 1,2,4- thiadiazoles parent nucleus The bipolarity compound that bonded fused ring system is formed is that a kind of conjugacy is higher, the low reflection of high refraction has good thermal stability Compound, be that a kind of ideal light takes out layer material.
In some embodiments of the invention, the compound has the structure of one of:
According to an embodiment of the invention, the compound with the above structure, to have 1,2, the 4- thiophenes for haling electronic capability Diazole is parent nucleus, is above attached by the lesser site N of cloud density of π bridge and fused ring system at its 3 and/or 5, On the one hand, the chain structure of D- π-A or D- π-A- π-D realize effective adjusting of molecular dipole moment, have asymmetric drawing electricity The thiadiazoles parent nucleus of sub- ability aligns orientation in intermolecular presentation, advantageously forms close-packed structure, improves heaped-up The refractive index of compound entirety under state；On the other hand, the thiadiazoles parent nucleus with larger proton number is at its 3 and/or 5 into one Step key even has different atomic number groups containing N, and the spin-orbit effect of electronics effectively increases suction of the molecule to light itself It receives, weakens the loss of light caused by light is totally reflected near cathode, improve device in current efficiency, function from physical layer The performance of rate efficiency, external quantum efficiency and coloration etc..In addition, the site N relatively active in π bridge and condensed hetero ring system carries out Connection, under the premise of reducing technology difficulty, effectively extends the length of molecule, improves the thermal stability of compound entirety, To effectively avoid thermal accumlation to the destruction of device architecture, effectively improves the non-radiative degree of coupling of device and use the longevity Life.In general, 1,2,4- thiadiazoles parent nucleus are bonded by the site N and condensed hetero ring system, and the compound of formation is a kind of proton The compound for having good thermal stability for counting the low reflection of larger, high refraction is that a kind of ideal light takes out layer material.
In some embodiments of the invention, the compound has the structure of one of:
According to an embodiment of the invention, the compound with the above structure, to have 1,2, the 4- thiophenes for haling electronic capability Diazole is parent nucleus, has the arylamine group of stronger electron donation in its 3 and/or 5 upper introducings, on the one hand, have high glass The introducing of the arylamine group of glass transition temperature improves the thermal stability of molecule entirety, effectively light is avoided to be converted into caused by heat Influence of the thermal accumlation to device lifetime and stability；On the other hand, the branched structure cross arrangement of arylamine forms intensive heap Product structure, with the asymmetric thiadiazoles core for drawing electronic capability row of orientation between the stronger branched structure of electron donating group Column, improve the refractive index of compound entirety under stacking states, to further promote device optical coupling output efficiency, improve device Part current efficiency, power efficiency, external quantum efficiency and in terms of comprehensive performance.In general, 1,2,4- thiophenes two Azoles parent nucleus in its 3 and/or 5 upper bonded arylamine groups with branched structure, the compound of formation be a kind of cross arrangement, The compound for having good thermal stability of dense accumulation is that a kind of ideal light takes out layer material.
It should be noted that, in this document, term " heteroaryl " refers on aromatic ring containing heteroatomic substituent group, such as pyrrole Piperidinyl.Term " aryloxy group ", " arylthio ", " aryl amine " meaning substituent group aromatic ring on do not contain hetero atom, but aromatic ring quilt Substituent group containing O, S or N replaces, such as the phenyl that methoxy-substituted phenyl, the sulfydryl phenyl, the amino that replace replace.
In another aspect of this invention, a kind of method that the present invention proposes compound for preparing above-described embodiment.According to this The embodiment of invention, this method comprises: compound shown in compound shown in compound, formula (b) shown in formula (a) and formula (c) connects Touching, to obtain the compound of above-described embodiment,
Wherein, Z1And Z2It is separately Cl or Br, R1And R2、L1、L2, d and e be foregoing.Using as a result, should Method can be effectively prepared to obtain the compound of above-described embodiment.
According to an embodiment of the invention, can react by Suzuki, chemical combination shown in compound, formula (b) shown in formula (a) is utilized Compound shown in object and formula (c) prepares the compound of the present invention.It is specific:
According to an embodiment of the invention, above-mentioned contact is there are the in the mixed solvents of palladium catalyst and alkali to carry out.Palladium The specific type of catalyst and alkali and the mixed solvent for being applicable in reaction are not particularly restricted, and those skilled in the art can be with It is selected according to actual needs.Preferred embodiment in accordance with the present invention, above-mentioned palladium catalyst can be [1,1 '-bis- (diphenyl At least one of phosphino-) ferrocene] palladium chloride, tetra-triphenylphosphine palladium, tris(dibenzylideneacetone) dipalladium and palladium acetate.On Stating alkali can be cesium carbonate, cesium fluoride, potassium fluoride, potassium carbonate, potassium phosphate, lithium phosphate, sodium carbonate, tetrabutylammonium and tertiary fourth At least one of sodium alkoxide.Above-mentioned mixed solvent may include toluene, dimethylbenzene, ethyl alcohol, N,N-dimethylformamide, N, N- diformazan At least one of yl acetamide and water.
It should be noted that being suitable for the prepare compound simultaneously described previously for feature and advantage described in compound Method, this is no longer going to repeat them.
It the method to prepare compound according to an embodiment of the present invention and is described in detail further below:
According to an embodiment of the invention, in compound shown in formula (a), Z1And Z2It is separately Cl or Br.According to this hair Bright preferred embodiment, Z1And Z2Simultaneously it is not Cl or is not simultaneously Br, as a result, using the difference of Cl and Br reactivity, Step by step by the Z in compound shown in compound of formula (a) shown in compound shown in formula (b) or formula (c)1And Z2Replaced.Specifically Ground can introduce R into compound shown in formula (a) according to the following formula1-(L1)dAnd R2-(L2)e:
According to an embodiment of the invention, under the action of palladium catalyst and alkali, R1-(L1)dAnd R2-(L2)eBoric acid chemical combination Object may replace the halogen in 1,2,4- thiadiazoles, thus by R1-(L1)dAnd R2-(L2)eIt is introduced into 1,2,4- thiadiazoles structure.Root According to specific embodiments of the present invention, in [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (PdCl2And carbonic acid (dppf)) Caesium (Cs2CO3) under the action of, boronic acid compounds are reacted with Cl first, subsequent in tetra-triphenylphosphine palladium (Pd (PPh3)4) and carbonic acid Potassium (K2CO3) under the action of, boronic acid compounds are reacted with Br, to complete R in 1,2,4- thiadiazoles structures1-(L1)dAnd R2- (L2)eIntroducing.
According to an embodiment of the invention, in formula (one) and formula (two) reaction, dihalide, the R of 1,2,4- thiadiazoles1- (L1)d-B(OH)2And cesium carbonate can be according to molar ratio 1:(1~1.5): (1~3) feeds intake, and suitable toluene is added, in nitrogen Under atmosphere, 1%~10% [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride is added (by the substance of dihalo object Meter), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, processing obtains R1-(L1)dIt is right One halides of the 1,2,4- thiadiazoles that should replace；Further, by R1-(L1)dOne halogen of the corresponding 1,2,4- thiadiazoles replaced For object and R2-(L2)e-B(OH)2And potassium carbonate is according to molar ratio 1:(1~1.5): (2~4) feed intake, be added suitable toluene, 1 ‰~1% tetrakis triphenylphosphine palladium (by the meter of the substance of a halides) is added under nitrogen atmosphere in second alcohol and water, rises Temperature to 50~100 DEG C of 4~48h of reaction, liquid phase monitoring reaction is completed, is cooled to room temperature, processing obtains final products.
Other embodiments according to the present invention, R1-(L1)dAnd R2-(L2)eIt can be the substituent group of identical structure, it can be with R is introduced into compound shown in formula (a) according to the following formula1And R2:
According to an embodiment of the invention, in formula (three) reaction, dihalide, the R of 1,2,4- thiadiazoles1-(L1)d-B (OH)2、R2-(L2)e-B(OH)2And potassium carbonate is according to molar ratio 1:(1~1.5): (1~1.5): (2~4) feed intake, and are added suitable Toluene, the second alcohol and water of amount, under nitrogen atmosphere, the tetrakis triphenylphosphine palladium of addition 1 ‰~1% is (by the substance of dihalo object Meter), be warming up to 50~100 DEG C of 4~48h of reaction, liquid phase monitoring reaction is completed, and is cooled to room temperature, processing is finally produced Product.
According to an embodiment of the invention, above-mentioned R1-(L1)d-B(OH)2、R2-(L2)e-B(OH)2It can make in following manner For (with R1ForPrepare R1-(L1)d-B(OH)2For):
In formula (four) reaction, (L1)dCorresponding halogenated boronic acid derivatives, R1Corresponding amine, sodium tert-butoxide (t-BuONa), Tri-tert-butylphosphine tetrafluoroborate (t-Bu3BF4P) according to molar ratio 1:(1~1.5): (2~4): (1 ‰~10 ‰) feed intake, and add Enter suitable toluene, under nitrogen atmosphere, 0.5 ‰~10 ‰ palladium acetate (Pd (OAc) is added2) (press (L1)dIt is corresponding halogenated The meter of the substance of boronic acid derivatives), 60~150 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, and room is cooled to Temperature, processing obtain R1-(L1)d-B(OH)2。
According to an embodiment of the invention, above-mentioned R1-(L1)d-B(OH)2、R2-(L2)e-B(OH)2It can also be in following manner Preparation is (with R1ForPrepare R1-(L1)d-B(OH)2For):
In formula (five) reaction, A2Corresponding halide, A1Corresponding aminate, sodium tert-butoxide (t-BuONa), three tertiary fourths Base phosphine tetrafluoroborate (t-Bu3BF4P) according to molar ratio 1:(1.5~3): (2~4): (0.5%~2%) feeds intake, and is added appropriate Toluene, under nitrogen atmosphere, be added 3 ‰~1% tris(dibenzylideneacetone) dipalladium (Pd2(dba)3)(A2Corresponding halogenation The meter of the substance of object), 80~150 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, 35~70 DEG C are cooled to, Addition and A under nitrogen atmosphere2(the L of the amount of the substances such as halide1)dCorresponding halogenated boronic acid derivatives, are warming up to 80~150 DEG C The reaction was continued 4~48h, processing obtain R1-(L1)d-B(OH)2。
In another aspect of the invention, the invention proposes a kind of electronic components.According to an embodiment of the invention, the electronics Element includes: photosphere, cathode and anode out, wherein it is described go out photosphere be formed in side table of the cathode far from the anode Face, the photosphere out are formed by the compound of above-described embodiment.
Electronic component according to an embodiment of the present invention goes out photosphere by using what the compound of above-described embodiment was formed, can The loss for effectively weakening light caused by light is totally reflected near cathode, improves device in current efficiency, power efficiency, outer amount The performance of sub- efficiency and coloration etc..
Meanwhile electronic component according to an embodiment of the present invention, using the compound of above-described embodiment as go out photosphere material, with It operates relatively simple and lesser material hot evaporation process is destroyed to device architecture, organic illuminating element is applied to, from physical layer Light in face of organic illuminating element 80% is improved in the loss problem of device inside, and the 1 of above-described embodiment, 2,4- thiadiazoles Class compound greatly improves its optical coupling output ability with its excellent refractive index and extinction coefficient, and then improves device The performance of luminous intensity, current efficiency, power efficiency, external quantum efficiency and the coloration of part etc., also, construct have compared with The material system of heat-flash stability effectively prevents destruction of the thermal accumlation to device architecture, improves the stability of device performance And service life.
According to an embodiment of the invention, in electronic component go out photosphere with a thickness of 1~100nm.It as a result, can be further advantageous In the performance of 1,2, the 4- aforementioned excellent properties of thiadiazole compound, to further increase device performance.
It should be noted that described previously for compound, prepare compound method described in feature and advantage simultaneously fit For the electronic component, this is no longer going to repeat them.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description Obviously, or practice through the invention is recognized.
Detailed description of the invention
Above-mentioned and/or additional aspect of the invention and advantage will become from the description of the embodiment in conjunction with the following figures Obviously and it is readily appreciated that, in which:
Fig. 1 is wavelength-luminous intensity performance diagram of A9 device and control group, blank group device；
Fig. 2 is the voltage-current density-luminosity response figure of A9 device and control group, blank group device；
Fig. 3 is current density-current efficiency-power efficiency characteristic curve of A9 device and control group, blank group device Figure；
Fig. 4 is brightness-external quantum efficiency characteristic curve graph of A9 device and control group, blank group device；
Fig. 5 is wavelength-refractive index curve chart of A9 device Yu control group device；
Fig. 6 is wavelength-luminous intensity performance diagram of B11 device and control group, blank group device；
Fig. 7 is the voltage-current density-luminosity response figure of B11 device and control group, blank group device；
Fig. 8 is current density-current efficiency-power efficiency characteristic curve of B11 device and control group, blank group device Figure；
Fig. 9 is brightness-external quantum efficiency characteristic curve graph of B11 device and control group, blank group device；
Figure 10 is wavelength-refractive index curve chart of B11 device Yu control group device；
Figure 11 is wavelength-luminous intensity performance diagram of C5 device and control group, blank group device；
Figure 12 is the voltage-current density-luminosity response figure of C5 device and control group, blank group device；
Figure 13 is current density-current efficiency-power efficiency characteristic curve of C5 device and control group, blank group device Figure；
Figure 14 is brightness-external quantum efficiency characteristic curve graph of C5 device and control group, blank group device；
Figure 15 is wavelength-refractive index curve chart of C5 device Yu control group device.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer, For can be with conventional products that are commercially available.
Embodiment 1
(1) in the there-necked flask of 500mL, the bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (19.94g, 100mmol), phenanthrene -9- are put into 200mL toluene is added in ylboronic acid (22.20g, 100mmol), cesium carbonate (48.87g, 150mmol), under nitrogen atmosphere, is added [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (1.46g, 2mmol), is warming up to 50~100 DEG C of 4~48h of reaction, liquid Mutually monitoring reaction is completed, and is cooled to room temperature, and is washed, and is filtered, and the bromo- 3- of 5- (phenanthrene -9- base)-can be obtained in concentration, pillar layer separation 1,2,4- thiadiazoles 25.25g, yield 74%；
(2) in the there-necked flask of 500mL, the investment bromo- 3- of 5- (phenanthrene -9- base) -1,2,4- thiadiazoles (17.06g, 50mmol), 4- tert-butylbenzeneboronic acid (8.90g, 50mmol), potassium carbonate (13.82g, 100mmol), addition 150mL toluene, 50mL ethyl alcohol and 50mL water are added tetrakis triphenylphosphine palladium (0.12g, 0.1mmol) under nitrogen atmosphere, are warming up to 50~100 DEG C 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filtering, final production can be obtained in pillar layer separation Product 17.16g, yield 87%.
Mass spectrograph MALDI-TOF-MS (m/z)=394.5352, theoretical molecular weight: 394.5360；Anal.Calcd for C26H22N2(%): C 79.15, H 5.62, N 7.10, Found:C 79.15, H 5.60, N 7.10.
Embodiment 2
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 17.62g, yield 85%. Mass spectrograph MALDI-TOF-MS (m/z)=414.5266, theoretical molecular weight: 414.5260；Anal.Calcd for C28H18N2 (%): C 81.13, H 4.38, N 6.67, Found:C 81.14, H 4.38, N 6.65.
Embodiment 3
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 20.52g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=506.6664, theoretical molecular weight: 506.6670；Anal.Calcd for C35H26N2 (%): C 82.97, H 5.17, N 5.53, Found:C 82.95, H 5.18, N 5.53.
Embodiment 4
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 18.62g, yield 89%. Mass spectrograph MALDI-TOF-MS (m/z)=418.5577, theoretical molecular weight: 418.5580；Anal.Calcd for C28H22N2 (%): C 80.35, H 5.30, N 6.69, Found:C 80.36, H 5.30, N 6.70.
Embodiment 5
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 18.20g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=438.5487, theoretical molecular weight: 438.5480；Anal.Calcd for C30H18N2 (%): C 82.16, H 4.14, N 6.39, Found:C 82.16, H 4.15, N 6.40.
Embodiment 6
In the there-necked flask of 500mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (19.94g, 50mmol), phenanthrene -3- base boron are put into 150mL toluene, 50mL ethyl alcohol and 50mL water is added, in nitrogen in acid (22.20g, 100mmol), potassium carbonate (13.82g, 100mmol) It under atmosphere is enclosed, is added tetrakis triphenylphosphine palladium (0.12g, 0.1mmol), is warming up to 85 DEG C of reaction 28h, liquid phase monitoring has been reacted At being cooled to room temperature, wash, filtering, final products 18.64g, yield 85% can be obtained in pillar layer separation.Mass spectrograph MALDI-TOF-MS (m/z)=438.5487, theoretical molecular weight: 438.5480；Anal.Calcd for C30H18N2(%): C 82.16,H 4.14,N 6.39,Found:C 82.15,H 4.14,N 6.41。
Embodiment 7
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 18.82g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=453.5624, theoretical molecular weight: 453.5630；Anal.Calcd for C30H19N3 (%): C 79.44, H 4.22, N 9.26, Found:C 79.45, H 4.23, N 9.26.
Embodiment 8
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 18.90g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=466.5625, theoretical molecular weight: 466.5620；Anal.Calcd for C30H18N4 (%): C 77.23, H 3.89, N 12.01, Found:C 77.23, H 3.90, N 12.00.
Embodiment 9
(1) in the there-necked flask of 500mL, (9H- carbazole -3- base) boric acid (25.32g, 150mmol), the bromo- 2- benzene of 5- are put into Yl pyrimidines (28.21g, 120mmol), sodium tert-butoxide (23.04g, 240mmol), tri-tert-butylphosphine tetrafluoroborate (0.21g, 0.72mmol), 250mL toluene is added, under nitrogen atmosphere, addition tris(dibenzylideneacetone) dipalladium (0.33g, 0.36mmol), 50~150 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, column (9- (2- phenyl pyrimidine -5- base) -9H- carbazole -3- base) boric acid 40.31g, yield 92% can be obtained in chromatographic isolation；
(2) in the there-necked flask of 500mL, the bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (19.94g, 100mmol), (9- are put into (2- phenyl pyrimidine -5- base) -9H- carbazole -3- base) boric acid (36.52g, 100mmol), cesium carbonate (48.87g, 150mmol), add Enter 200mL toluene, under nitrogen atmosphere, addition [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (1.46g, 2mmol), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filter, concentration, The bromo- 3- of 5- (9- (2- phenyl pyrimidine -5- base) -9H- carbazole -4- base) -1,2,4- thiadiazoles can be obtained in pillar layer separation 34.87g yield 72%；
(3) in the there-necked flask of 500mL, the bromo- 3- of 5- (9- (2- phenyl pyrimidine -5- base) -9H- carbazole -4- base) -1 is put into, 2,4- thiadiazoles (24.22g, 50mmol), (3- (naphthalene -1- base) phenyl) boric acid (12.40g, 50mmol), potassium carbonate (13.82g, 100mmol), 150mL toluene, 50mL ethyl alcohol and 50mL water is added, under nitrogen atmosphere, tetrakis triphenylphosphine palladium is added (0.12g, 0.1mmol), is warming up to 50~100 DEG C of 4~48h of reaction, and liquid phase monitoring reaction is completed, is cooled to room temperature, washes, mistake Final products 25.83g, yield 85% can be obtained in filter, pillar layer separation.
Mass spectrograph MALDI-TOF-MS (m/z)=607.7348, theoretical molecular weight: 607.7350；Anal.Calcd for C40H25N5(%): C 79.05, H 4.15, N 11.52, Found:C 79.05, H 4.17, N 11.51.
Embodiment 10
The target compound in above formula, which is prepared, according to method same as Example 9 (is compared to embodiment 9, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 23.91g, yield 87%. Mass spectrograph MALDI-TOF-MS (m/z)=549.6914, theoretical molecular weight: 549.6920；Anal.Calcd for C36H27N3 (%): C 78.66, H 4.95, N 7.64, Found:C 78.66, H 4.93, N 7.65.
Embodiment 11
The target compound in above formula, which is prepared, according to method same as Example 9 (is compared to embodiment 9, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 20.69g, yield 82%. Mass spectrograph MALDI-TOF-MS (m/z)=504.6114, theoretical molecular weight: 504.6110；Anal.Calcd for C33H20N4 (%): C 78.55, H 4.00, N 11.10, Found:C 78.56, H 4.00, N 11.10.
Embodiment 12
(1) in the there-necked flask of 500mL, (9H- carbazole -3- base) boric acid (25.32g, 120mmol), 3- bromine hexichol is put into Bithiophene (31.58g, 120mmol), sodium tert-butoxide (23.04g, 240mmol), tri-tert-butylphosphine tetrafluoroborate (0.21g, 0.72mmol), 250mL toluene is added, under nitrogen atmosphere, addition tris(dibenzylideneacetone) dipalladium (0.33g, 0.36mmol), 115 DEG C of reaction 16h are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, column chromatography point From (9- (dibenzothiophenes -3- base) -9H- carbazole -3- base) boric acid 38.70g, yield 82% can be obtained；
(2) in the there-necked flask of 500mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (19.94g, 50mmol), (9- (two are put into Benzothiophene -3- base) -9H- carbazole -3- base) boric acid (39.33g, 100mmol), potassium carbonate (13.82g, 100mmol), it is added 150mL toluene, 50mL ethyl alcohol and 50mL water are added tetrakis triphenylphosphine palladium (0.12g, 0.1mmol) under nitrogen atmosphere, rise Temperature to 85 DEG C of reaction 28h, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, and filtering, pillar layer separation can be obtained final Product 32.02g, yield 82%.
Mass spectrograph MALDI-TOF-MS (m/z)=780.9815, theoretical molecular weight: 780.9820；Anal.Calcd for C50H28N4(%): C 76.90, H 3.61, N 7.17, Found:C 76.90, H 3.60, N 7.18.
Embodiment 13
The target compound in above formula, which is prepared, according to method same as Example 9 (is compared to embodiment 9, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical).Obtain final product 30.54g, yield 82%. Mass spectrograph MALDI-TOF-MS (m/z)=744.9156, theoretical molecular weight: 744.9160；Anal.Calcd for C52H32N4 (%): C 83.84, H 4.33, N 7.52, Found:C 83.85, H 4.34, N 7.52.
Embodiment 14
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 19.09g, yield 84%. Mass spectrograph MALDI-TOF-MS (m/z)=454.5473, theoretical molecular weight: 454.5470；Anal.Calcd for C30H18N2 (%): C 79.27, H 3.99, N 6.16, Found:C 79.26, H 3.40, N 6.16.
Embodiment 15
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 23.14g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=557.6748, theoretical molecular weight: 557.6750；Anal.Calcd for C36H23N5 (%): C 77.54, H 4.16, N 12.56, Found:C 77.54, H 4.15, N 12.56.
Embodiment 16
The target compound in above formula, which is prepared, according to method same as Example 6 (is compared to embodiment 6, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 19.76g, yield 84%. Mass spectrograph MALDI-TOF-MS (m/z)=470.6337, theoretical molecular weight: 470.6340；Anal.Calcd for C32H26N2 (%): C 81.67, H 5.57, N 5.95, Found:C 81.66, H 5.58, N 5.95.
Embodiment 17
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 23.11g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=570.7264, theoretical molecular weight: 570.7280；Anal.Calcd for C38H22N2 (%): C 79.97, H 3.89, N 4.91, Found:C 79.97, H 3.90, N 4.89.
Embodiment 18
(1) in the there-necked flask of 500mL, bromo- 5, the 10- dihydrophenazine (23.50g, 90mmol) of investment 2-, bromobenzene (28.26g, 180mmol), sodium tert-butoxide (17.28g, 180mmol), tri-tert-butylphosphine tetrafluoroborate (0.16g, 0.55mmol), 250mL toluene is added, under nitrogen atmosphere, is added palladium acetate (0.06g, 0.27mmol), is warming up to 50~150 DEG C reaction 4~48h, liquid phase monitoring reaction complete, be cooled to room temperature, be added 125mL petroleum ether, filtering, solid hexane and two The mixed liquor of chloromethanes is beaten one time, and bromo- 5,10- diphenyl -5, the 10- dihydrophenazine 32.36g of 2-, yield 87% can be obtained；
(2) in the there-necked flask of 500mL, addition bromo- 5,10- diphenyl -5, the 10- dihydrophenazine of 2- (28.93g, 70mmol), 200mL tetrahydrofuran after stirring and dissolving, under nitrogen protection, is cooled to -78 DEG C, dropwise with constant pressure funnel 15mL n-BuLi is added, after adding reaction 45min, is added trimethylborate (15.58g, 150mmol), restores after reacting 1h To room temperature the reaction was continued 10h, after being cooled to 0 DEG C, reaction is hydrolyzed in the aqueous hydrochloric acid solution 100mL that 1.0M is added, and uses dichloromethane (5,10- diphenyl -5,10- dihydrophenazine -2- base) boric acid 21.18g, yield 80% can be obtained in alkane extraction, concentration；
(3) in the there-necked flask of 250mL, the bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (9.97g, 50mmol), (5,10- are put into Diphenyl -5,10- dihydrophenazine -2- base) boric acid (18.91g, 50mmol), cesium carbonate (24.43g, 75mmol), 100mL is added Toluene is added [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.73g, 1mmol), is warming up under nitrogen atmosphere 50~100 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filter, concentration, pillar layer separation, i.e., The bromo- 3- of 5- (5,10- diphenyl -5,10- dihydrophenazine -2- base) -1,2,4- thiadiazoles 17.66g, yield 71% can be obtained；
(4) in the there-necked flask of 250mL, the bromo- 3- of 5- (5,10- diphenyl -5,10- dihydrophenazine -2- base) -1,2 is put into, 4- thiadiazoles (12.43g, 25mmol), 4- tert-butylbenzeneboronic acid (4.45g, 25mmol), potassium carbonate (6.91g, 50mmol), add Enter 80mL toluene, 40mL ethyl alcohol and 40mL water, under nitrogen atmosphere, be added tetrakis triphenylphosphine palladium (0.06g, 0.05mmol), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, pillar layer separation, i.e., Final products 11.98g, yield 87% can be obtained.
Mass spectrograph MALDI-TOF-MS (m/z)=550.7247, theoretical molecular weight: 550.7240；Anal.Calcd for C36H30N4(%): C 78.51, H 5.49, N 10.17, Found:C 78.50, H 5.50, N 10.17.
Embodiment 19
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 12.34g, yield 83%.Mass spectrograph MALDI-TOF-MS (m/z)=594.7366, theoretical molecular weight: 594.7360；Anal.Calcd for C40H26N4(%): C 80.78, H 4.41, N 9.42, Found:C 80.79, H 4.40, N 9.42.
Embodiment 20
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 14.42g, yield 86%.Mass spectrograph MALDI-TOF-MS (m/z)=670.8332, theoretical molecular weight: 670.8340；Anal.Calcd for C46H30N4(%): C 82.36, H 4.51, N 8.35, Found:C 82.36, H 4.50, N 8.35.
Embodiment 21
(1) in the there-necked flask of 500mL, bromo- 5, the 10- dihydrophenazine (23.50g, 90mmol) of investment 2-, bromobenzene (28.26g, 180mmol), sodium tert-butoxide (17.28g, 180mmol), tri-tert-butylphosphine tetrafluoroborate (0.16g, 0.55mmol), 250mL toluene is added, under nitrogen atmosphere, is added palladium acetate (0.06g, 0.27mmol), is warming up to 115 DEG C instead Answer 10h, liquid phase monitoring reaction is completed, and is cooled to room temperature, it is added 125mL petroleum ether, filtering, solid hexane and methylene chloride Mixed liquor is beaten one time, and bromo- 5,10- diphenyl -5, the 10- dihydrophenazine 32.36g of 2-, yield 87% can be obtained；
(2) in the there-necked flask of 500mL, addition bromo- 5,10- diphenyl -5, the 10- dihydrophenazine of 2- (28.93g, 70mmol), 200mL tetrahydrofuran after stirring and dissolving, under nitrogen protection, is cooled to -78 DEG C, dropwise with constant pressure funnel 15mL n-BuLi is added, after adding reaction 45min, is added trimethylborate (15.58g, 150mmol), restores after reacting 1h To room temperature the reaction was continued 10h, after being cooled to 0 DEG C, reaction is hydrolyzed in the aqueous hydrochloric acid solution 100mL that 1.0M is added, and uses dichloromethane (5,10- diphenyl -5,10- dihydrophenazine -2- base) boric acid 21.18g, yield 80% can be obtained in alkane extraction, concentration.
(3) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (9.97g, 25mmol), (5,10- are put into Diphenyl -5,10- dihydrophenazine -2- base) boric acid (18.91g, 50mmol), potassium carbonate (6.91g, 50mmol), 80mL first is added Benzene, 40mL ethyl alcohol and 40mL water are added tetrakis triphenylphosphine palladium (0.06g, 0.05mmol) under nitrogen atmosphere, are warming up to 85 DEG C reaction 28h, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filtering, final products can be obtained in pillar layer separation 15.95g yield 85%.
Mass spectrograph MALDI-TOF-MS (m/z)=750.9235, theoretical molecular weight: 750.9240；Anal.Calcd for C50H34N6(%): C 79.97, H 4.56, N 11.19, Found:C 79.99, H 4.55, N 11.20.
Embodiment 22
According to method identical with embodiment 21 prepare in above formula target compound (be compared to embodiment 21, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final products 15.64g, yield 84%.Mass spectrograph MALDI-TOF-MS (m/z)=745.0347, theoretical molecular weight: 745.0340；Anal.Calcd for C46H40N4(%): C 74.16, H 5.41, N 7.52, Found:C 74.15, H 5.39, N 7.52.
Embodiment 23
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 13.23g, yield 83%.Mass spectrograph MALDI-TOF-MS (m/z)=637.8193, theoretical molecular weight: 637.8190；Anal.Calcd for C42H27N3(%): C 79.09, H 4.27, N 6.59, Found:C 79.10, H 4.27, N 6.60.
Embodiment 24
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 12.42g, yield 86%.Mass spectrograph MALDI-TOF-MS (m/z)=577.7996, theoretical molecular weight: 577.7900；Anal.Calcd for C39H35N3(%): C 81.07, H 6.11, N 7.27, Found:C 81.06, H 6.10, N 7.27.
Embodiment 25
The target compound prepared in above formula in the same manner as shown in Example 1 (is compared to embodiment 1, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 17.82g, yield 86%. Mass spectrograph MALDI-TOF-MS (m/z)=414.5267, theoretical molecular weight: 414.5260；Anal.Calcd for C28H18N2 (%): C 81.13, H 4.38, N 6.76, Found:C 81.12, H 4.40, N 6.76.
Embodiment 26
The target compound in above formula, which is prepared, according to method same as Example 6 (is compared to embodiment 6, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 19.71g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=486.5917, theoretical molecular weight: 486.5920；Anal.Calcd for C34H18N2 (%): C 83.93, H 3.73, N 5.76, Found:C 83.92, H 3.75, N 5.75.
Embodiment 27
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 9.69g, yield 87%. Mass spectrograph MALDI-TOF-MS (m/z)=445.5846, theoretical molecular weight: 445.5840；Anal.Calcd for C29H23N3 (%): C 78.17, H 5.20, N 9.43, Found:C 78.15, H 5.20, N 9.42.
Embodiment 28
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 12.46g, yield 82%.Mass spectrograph MALDI-TOF-MS (m/z)=607.8335, theoretical molecular weight: 607.8340；Anal.Calcd for C39H33N3(%): C 77.07, H 5.47, N 6.91, Found:C 77.07, H 5.48, N 6.90.
Embodiment 29
The target compound in above formula, which is prepared, according to method same as Example 9 (is compared to embodiment 9, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 26.13g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=629.7807, theoretical molecular weight: 629.7810；Anal.Calcd for C44H27N3 (%): C 83.92, H 4.32, N 6.67, Found:C 83.92, H 4.30, N 6.68.
Embodiment 30
According to method identical with embodiment 18 prepare in above formula target compound (be compared to embodiment 18, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 12.47g, yield 84%.Mass spectrograph MALDI-TOF-MS (m/z)=593.7038, theoretical molecular weight: 593.7040；Anal.Calcd for C40H23N3(%): C 80.92, H 3.90, N 7.08, Found:C 80.90, H 3.90, N 7.09.
Embodiment 31
The target compound in above formula, which is prepared, according to method substantially the same manner as Example 1 (is compared to embodiment 1, often The reactant of one corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 16.96g, yield 86%.Mass spectrograph MALDI-TOF-MS (m/z)=394.5095, theoretical molecular weight: 394.5100；Anal.Calcd for C24H14N2(%): C 73.07, H 3.58, N 7.10, Found:C 73.06, H 3.60, N 7.10.
Embodiment 32
The target compound in above formula, which is prepared, according to method same as Example 9 (is compared to embodiment 9, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 25.36g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=603.7430, theoretical molecular weight: 603.7430；Anal.Calcd for C42H25N3 (%): C 83.56, H 4.17, N 6.96, Found:C 83.55, H 4.19, N 6.96.
Embodiment 33
According to method identical with embodiment 21 prepare in above formula target compound (be compared to embodiment 21, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final products 15.24g, yield 81%.Mass spectrograph MALDI-TOF-MS (m/z)=752.9806, theoretical molecular weight: 752.9800；Anal.Calcd for C52H40N4(%): C 82.95, H 5.35, N 7.44, Found:C 82.94, H 5.35, N 7.45.
Embodiment 34
According to method identical with embodiment 12 prepare in above formula target compound (be compared to embodiment 12, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final products 28.09g, yield 84%.Mass spectrograph MALDI-TOF-MS (m/z)=668.8177, theoretical molecular weight: 668.8180；Anal.Calcd for C46H28N4(%): C 82.61, H 4.22, N 8.38, Found:C 82.60, H 4.24, N 8.38.
Embodiment 35
By tin indium oxide (ITO) glass substrate in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, Zhi Houxian Continued to be cleaned by ultrasonic 15min with acetone and isopropanol afterwards, be dried in vacuo 2h (105 DEG C), at the UV ozone of followed by 15min Reason, is sent to vacuum evaporation plating machine for ito glass substrate.
By molybdenum trioxide (MoO3) vacuum deposition ito glass substrate up to 10nm thickness formed hole injection layer.
By N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines (NPB) vacuum deposition are infused in hole The thickness for entering layer up to 60nm forms hole transmission layer.
By (9H- carbazole -9- base) benzene (mCP) (as luminescent layer material of main part) of 1,3- bis- and 4,4 '-bis- (9- ethyl -3- Carbazole vinyl) -1,1 '-biphenyl (BCzVBi) (as luminescent layer guest materials) exist with the common vacuum deposition of the weight ratio of 95:5 Hole transmission layer forms luminescent layer up to the thickness of 20nm.
By 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) vacuum deposition on the light-emitting layer to 30nm's Thickness forms electron transport layer materials.
Lithium fluoride (LiF) vacuum deposition is formed into electron injecting layer to the thickness of 1nm on the electron transport layer.
Aluminium (Al) vacuum deposition is formed into cathode up to the thickness of 100nm in electron injecting layer.
The compound vacuum deposition that embodiment 2,4,6,7~12,14,15,17~19,21~34 is prepared is respectively adopted Photosphere material is formed out up to the thickness of 60nm in cathode, to complete the preparation of organic illuminating element.To the luminous member of preparation Part carries out performance detection, and Fig. 1~4 are respectively wavelength-luminous intensity characteristic curve of A9 device and control group, blank group device Figure, voltage-current density-luminosity response figure, current density-current efficiency-power efficiency characteristic curve graph and brightness-are outer Quantum efficiency characteristic curve graph, Fig. 5 are wavelength-refractive index curve chart of A9 device and control group device.Specific detection data It is shown in Table 1:
1 organic electroluminescence device performance characterization of table
Testing result shows that the compound that Examples 1 to 34 is prepared shines as what photosphere material out was prepared Element current efficiency, power efficiency, external quantum efficiency and in terms of there is excellent performance, and be significantly better than control group (device number D, using TPBi as electron transfer layer and out photosphere material simultaneously) and blank group (device number K).In addition, S is former The asymmetric 1,2,4- thiadiazoles for having high thermal stability and have higher heat-staple rigidity that the introducing of son is formed The synergistic effect such as group, carbazole group, has further ensured the thermal stability of overall molecule, has improved the service life of device.
Embodiment 36
(1) in the there-necked flask of 500mL, the bromo- 9H- carbazole (24.61g, 100mmol) of investment 3-, naphthalene -2- ylboronic acid 250mL toluene is added in (17.20g, 100mmol), potassium carbonate (27.64g, 200mmol), under nitrogen atmosphere, is added four (three Phenylphosphine) palladium (0.23g, 0.2mmol), 50~150 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, and room is cooled to Temperature is washed, and 3- (naphthalene -2- base) -9H- carbazole 23.76g, yield 81% can be obtained in filtering, pillar layer separation；
(2) in the there-necked flask of 500mL, 3- (naphthalene -2- base) -9H- carbazole (17.60g, 60mmol), (4- bromobenzene is put into Base) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol), 200mL toluene is added, under nitrogen atmosphere, is added palladium acetate (0.03g, 0.12mmol), is warming up to 50~150 DEG C 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filtering, ((4- (3- can be obtained in pillar layer separation (naphthalene -2- base) -9H- carbazole -9- base) phenyl) boric acid 21.82g, yield 88%；
(3) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), ((4- (3- are put into (naphthalene -2- base) -9H- carbazole -9- base) phenyl) boric acid (12.40g, 30mmol), cesium carbonate (14.66g, 45mmol), it is added [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.44g, 6mmol) is added under nitrogen atmosphere in 120mL toluene, It is warming up to 90 DEG C of reactions for 24 hours, liquid phase monitoring reaction is completed, and it is cooled to room temperature, washes, filter, concentration, pillar layer separation Obtain the bromo- 5- of 3- (4- (3- (naphthalene -2- base) -9H- carbazole -9- base) phenyl) -1,2,4- thiadiazoles 12.30g, yield 77%；
(4) in the there-necked flask of 250mL, the bromo- 5- of 3- (4- (3- (naphthalene -2- base) -9H- carbazole -9- base) phenyl) -1 is put into, 2,4- thiadiazoles (5.32g, 10mmol), naphthalene -2- ylboronic acid (1.72g, 10mmol), potassium carbonate (2.76g, 20mmol) are added 50mL toluene, 25mL ethyl alcohol and 25mL water are added tetrakis triphenylphosphine palladium (0.02g, 0.02mmol) under nitrogen atmosphere, rise Temperature to 50~100 DEG C of 4~48h of reaction, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, pillar layer separation Obtain final products 4.70g, yield 81%.
Mass spectrograph MALDI-TOF-MS (m/z)=579.7204, theoretical molecular weight: 579.7210；Anal.Calcd for C40H25N3(%): C 82.87, H 4.35, N 7.25, Found:C 82.86, H 4.35, N 7.25.
Embodiment 37
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 6.43g, yield 79%.Matter Spectrometer MALDI-TOF-MS (m/z)=814.0366, theoretical molecular weight: 814.0370；Anal.Calcd for C56H35N3 (%): C 82.63, H 4.33, N 5.16, Found:C 82.64, H 4.34, N 5.15.
Embodiment 38
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 6.04g, yield 86%.Matter Spectrometer MALDI-TOF-MS (m/z)=701.8877, theoretical molecular weight: 701.8880；Anal.Calcd for C48H35N3 (%): C 82.14, H 5.03, N 5.99, Found:C 82.14, H 5.02, N 6.00.
Embodiment 39
(1) in the there-necked flask of 500mL, 9,9- dimethyl -9,10- acridan (12.56g, 60mmol), (3- are put into Bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine tetrafluoroborate 200mL toluene is added in (0.07g, 0.24mmol), under nitrogen atmosphere, is added palladium acetate (0.03g, 0.12mmol), is warming up to 50~150 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, and 50~200mL petroleum ether, filtering, solid is added It is beaten one time with the mixed liquor of hexane and methylene chloride, (3- (- 10 (9H)-yl of 9,9- dimethyl acridinium) phenyl) boron can be obtained Sour 17.38g, yield 88%；
(2) in the there-necked flask of 250mL, the investment bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), (3- (9, 9- dimethyl acridinium -10 (9H)-yl) phenyl) boric acid (9.88g, 30mmol), cesium carbonate (14.66g, 45mmol), it is added [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.44g, 6mmol) is added under nitrogen atmosphere in 120mL toluene, 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filter, concentration, column chromatography point From the bromo- 3- of 5- (3- (- 10 (9H)-yl of 9,9- dimethyl acridinium) phenyl) -1,2,4- thiadiazoles 10.36g, yield can be obtained 77%；
(3) in the there-necked flask of 250mL, the bromo- 3- of 5- (3- (- 10 (9H)-yl of 9,9- dimethyl acridinium) phenyl) -1 is put into, 2,4- thiadiazoles (4.48g, 10mmol), (3- (naphthalene -1- base) phenyl) boric acid (2.48g, 10mmol), potassium carbonate (2.76g, 20mmol), 20~80mL toluene, 20~50mL ethyl alcohol and 20~50mL water is added, under nitrogen atmosphere, four (triphenyls are added Phosphine) palladium (0.02g, 0.02mmol), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, Final products 6.04g, yield 86% can be obtained in washing, filtering, pillar layer separation.
Mass spectrograph MALDI-TOF-MS (m/z)=571.7424, theoretical molecular weight: 571.7420；Anal.Calcd for C39H29N3(%): C 81.93, H 5.11, N 7.35, Found:C 81.94, H 5.10, N 7.35.
Embodiment 40
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.93g, yield 82%.Matter Spectrometer MALDI-TOF-MS (m/z)=723.8973, theoretical molecular weight: 723.8980；Anal.Calcd for C49H33N5 (%): C 81.30, H 4.60, N 9.67, Found:C 81.30, H 4.58, N 9.68.
Embodiment 41
(1) in the there-necked flask of 500mL, 9,9- dimethyl -9,10- acridan (12.56g, 60mmol), (3- are put into Bromophenyl) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine tetrafluoroborate 200mL toluene is added in (0.07g, 0.24mmol), under nitrogen atmosphere, is added palladium acetate (0.03g, 0.12mmol), is warming up to 50~150 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, and 100mL petroleum ether, filtering are added, solid uses oneself The mixed liquor of alkane and methylene chloride is beaten one time, and (3- (- 10 (9H)-yl of 9,9- dimethyl acridinium) phenyl) boric acid can be obtained 17.38g yield 88%；
(2) in the there-necked flask of 500mL, the investment bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), (3- (9, 9- dimethyl acridinium -10 (9H)-yl) phenyl) boric acid (19.75g, 60mmol), potassium carbonate (8.28g, 60mmol), addition 50~ 200mL toluene, 50~100mL ethyl alcohol and 50~100mL water, under nitrogen atmosphere, addition tetrakis triphenylphosphine palladium (0.07g, 0.06mmol), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, column Final products 16.65g, yield 85% can be obtained in chromatographic isolation.
Mass spectrograph MALDI-TOF-MS (m/z)=652.8597, theoretical molecular weight: 652.8600；Anal.Calcd for C44H36N4(%): C 80.95, H 5.56, N 8.58, Found:C 80.95, H 5.55, N 8.58.
Embodiment 42
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.81g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=600.7575, theoretical molecular weight: 600.7580；Anal.Calcd for C38H24N4 (%): C 75.97, H 4.03, N 9.33, Found:C 75.98, H 4.03, N 9.34.
Embodiment 43
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.58g, yield 84%.Matter Spectrometer MALDI-TOF-MS (m/z)=545.6608, theoretical molecular weight: 545.6600；Anal.Calcd for C36H23N3 (%): C 79.24, H 4.25, N 7.70, Found:C 79.24, H 4.27, N 7.70.
Embodiment 44
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.89g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=611.7625, theoretical molecular weight: 611.7630；Anal.Calcd for C41H29N3 (%): C 80.50, H 4.78, N 6.87, Found:C 80.48, H 4.78, N 6.88.
Embodiment 45
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.74g, yield 86%.Matter Spectrometer MALDI-TOF-MS (m/z)=667.8883, theoretical molecular weight: 667.8890；Anal.Calcd for C44H33N3 (%): C 79.13, H 4.98, N 6.29, Found:C 79.12, H 5.00, N 6.29.
Embodiment 46
According to method identical with embodiment 41 prepare in above formula target compound (be compared to embodiment 41, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.50g, yield 87%. Mass spectrograph MALDI-TOF-MS (m/z)=632.8177, theoretical molecular weight: 632.8180；Anal.Calcd for C38H24N4 (%): C 72.12, H 3.82, N 8.85, Found:C 72.12, H 3.84, N 8.84.
Embodiment 47
(1) it in 500mL reaction flask, is added 10H- phenthazine (19.93g, 100mmol), methylene chloride (200mL), double Oxygen water (20mL), acetic acid (100mL) are warming up to 50~100 DEG C, react 4~48h, and liquid phase monitors 10H- phenthazine without residue, drop Temperature stops reaction.With silica gel funnel filtering reacting liquid, filtered fluid washing is layered, and 10H- dioxy phenthazine can be obtained in concentration 20.81g yield 90%；
(2) in the there-necked flask of 500mL, 10H- dioxy phenthazine (13.88g, 60mmol), (6- bromonaphthalene -2- base) are put into Boric acid (15.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol), 50~200mL toluene is added, under nitrogen atmosphere, is added palladium acetate (0.03g, 0.12mmol), is warming up to 50 ~150 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, and 100mL petroleum ether, filtering, solid hexane is added It is beaten one time with the mixed liquor of methylene chloride, (6- (10H- dioxy phenthazine -10- base) naphthalene -2- base) boric acid can be obtained 18.54g yield 77%；
(3) in the there-necked flask of 250mL, the bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), (6- are put into (10H- dioxy phenthazine -10- base) naphthalene -2- base) boric acid (12.04g, 30mmol), cesium carbonate (14.66g, 45mmol), it is added [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.44g, 6mmol) is added under nitrogen atmosphere in 120mL toluene, 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filter, concentration, column chromatography point From 10- (6- (bromo- 1,2,4- thiadiazoles -3- base of 5-) naphthalene -2- base) -10H- dioxy phenthazine 10.93g, yield can be obtained 70%；
(4) in the there-necked flask of 250mL, 10- (6- (bromo- 1,2,4- thiadiazoles -3- base of 5-) naphthalene -2- base) -10H- is put into Dioxy phenthazine (5.20g, 10mmol), [1,1 '-biphenyl] -3- ylboronic acid (1.98g, 10mmol), potassium carbonate (2.76g, 20mmol), 50mL toluene, 25mL ethyl alcohol and 25mL water is added, under nitrogen atmosphere, addition tetrakis triphenylphosphine palladium (0.02g, 0.02mmol), 50~100 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, filtering, column Final products 4.98g, yield 84% can be obtained in chromatographic isolation.
Mass spectrograph MALDI-TOF-MS (m/z)=593.7187, theoretical molecular weight: 593.7190；Anal.Calcd for C36H23N3(%): C 72.83, H 3.90, N 7.08, Found:C 72.82, H 3.90, N 7.09.
Embodiment 48
According to method identical with embodiment 47 prepare in above formula target compound (be compared to embodiment 47, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.15g, yield 80%. Mass spectrograph MALDI-TOF-MS (m/z)=643.7787, theoretical molecular weight: 643.7790；Anal.Calcd for C40H25N3 (%): C 74.63, H 3.91, N 6.53.Found:C 74.63, H 3.90, N 6.55.
Embodiment 49
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.98g, yield 84%.Matter Spectrometer MALDI-TOF-MS (m/z)=594.7353, theoretical molecular weight: 594.7360；Anal.Calcd for C40H26N4 (%): C 80.78, H 4.41, N 9.42, Found:C 80.77, H 4.40, N 9.42.
Embodiment 50
(1) in 500mL there-necked flask, be added 5,10- dihydrophenazine (29.15g, 160mmol), bromobenzene (23.55g, 150mmol), sodium tert-butoxide (28.80g, 300mmol), tri-tert-butylphosphine tetrafluoroborate (0.18g, 0.6mmol), 250mL Toluene is added palladium acetate (0.06g, 0.3mmol) under nitrogen atmosphere, is warming up to 50~150 DEG C, reacts 4~48h, liquid phase prison It surveys reaction to complete, be cooled to room temperature, wash, filter, 5- phenyl -5,10- dihydrophenazine can be obtained in concentration, pillar layer separation 21.70g yield 56%；
(2) in the there-necked flask of 500mL, 5- phenyl -5,10- dihydrophenazine (15.50g, 60mmol), (4- bromobenzene are put into Base) boric acid (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine (0.07g, 0.24mmol), add Enter 200mL toluene, under nitrogen atmosphere, be added palladium acetate (0.03g, 0.12mmol), be warming up to 50~150 DEG C reaction 4~ 48h, liquid phase monitoring reaction are completed, are cooled to room temperature, and are added 100mL petroleum ether, filtering, solid hexane and methylene chloride it is mixed It closes liquid to be beaten one time, (4- (10- azophenlyene -5 (10H)-yl) phenyl) boric acid 19.06g, yield 84% can be obtained；
(3) in the there-necked flask of 250mL, the bromo- 3- of 5- chloro- 1,2,4- thiadiazoles (1.99g, 10mmol), (4- (10- are put into Azophenlyene -5 (10H)-yl) phenyl) boric acid (7.56g, 20mmol), potassium carbonate (2.76g, 20mmol), 50mL toluene, 25mL is added Ethyl alcohol and 25mL water are added tetrakis triphenylphosphine palladium (0.02g, 0.02mmol) under nitrogen atmosphere, are warming up to 50~100 DEG C 4~48h is reacted, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, final products can be obtained in filtering, pillar layer separation 4.98g, yield 84%.
Mass spectrograph MALDI-TOF-MS (m/z)=750.9247, theoretical molecular weight: 750.9240；Anal.Calcd for C50H34N6(%): C 79.97, H 4.56, N 11.19, Found:C 79.98, H 4.56, N 11.20.
Embodiment 51
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.29g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=661.8412, theoretical molecular weight: 661.8410；Anal.Calcd for C44H27N3 (%): C 79.85, H 4.11, N 6.35, Found:C 79.86, H 4.10, N 6.35.
Embodiment 52
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.44g, yield 83%.Matter Spectrometer MALDI-TOF-MS (m/z)=655.8185, theoretical molecular weight: 655.8190；Anal.Calcd for C46H29N3 (%): C 84.25, H 4.46, N 6.41, Found:C 84.25, H 4.45, N 6.40.
Embodiment 53
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.02g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=503.6234, theoretical molecular weight: 503.6230；Anal.Calcd for C34H21N3 (%): C 81.09, H 4.20, N 8.34, Found:C 81.08, H 4.20, N 8.35.
Embodiment 54
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.60g, yield 81%.Matter Spectrometer MALDI-TOF-MS (m/z)=691.8844, theoretical molecular weight: 691.8850；Anal.Calcd for C44H25N3 (%): C 76.38, H 3.64, N 6.07, Found:C 76.38, H 3.66, N 6.06.
Embodiment 55
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.04g, yield 85%.Matter Spectrometer MALDI-TOF-MS (m/z)=475.6097, theoretical molecular weight: 475.6100；Anal.Calcd for C30H25N3 (%): C 75.76, H 5.30, N 8.84, Found:C 75.76, H 5.32, N 8.82.
Embodiment 56
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 6.40g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=799.9927, theoretical molecular weight: 799.9920；Anal.Calcd for C56H37N3 (%): C 84.08, H 4.66, N 5.25, Found:C 84.08, H 4.67, N 5.23.
Embodiment 57
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.58g, yield 85%.Matter Spectrometer MALDI-TOF-MS (m/z)=545.6600, theoretical molecular weight: 545.6600；Anal.Calcd for C36H23N3 (%): C 79.24, H 4.25, N 7.70, Found:C 79.23, H 4.27, N 7.70.
Embodiment 58
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.47g, yield 82%.Matter Spectrometer MALDI-TOF-MS (m/z)=545.7046, theoretical molecular weight: 545.7040；Anal.Calcd for C37H27N3 (%): C 81.44, H 4.99, N 7.70, Found:C 81.45, H 5.00, N 7.70.
Embodiment 59
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.48g, yield 80%.Matter Spectrometer MALDI-TOF-MS (m/z)=685.8893, theoretical molecular weight: 685.8890；Anal.Calcd for C48H35N3 (%): C 84.06, H 5.14, N 6.13, Found:C 84.05, H 5.15, N 6.14.
Embodiment 60
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.59g, yield 82%.Matter Spectrometer MALDI-TOF-MS (m/z)=559.7047, theoretical molecular weight: 559.7050；Anal.Calcd for C36H21N3 (%): C 77.25, H 3.78, N 7.51, Found:C 77.25, H 3.80, N 7.50.
Embodiment 61
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.98g, yield 84%.Matter Spectrometer MALDI-TOF-MS (m/z)=646.8122, theoretical molecular weight: 646.8120；Anal.Calcd for C44H30N4 (%): C 81.71, H 4.68, N 8.66, Found:C 81.70, H 4.69, N 8.66.
Embodiment 62
The target product in above formula, which is prepared, according to method identical with embodiment 36 (is compared to embodiment 36, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.07g, yield 83%.Matter Spectrometer MALDI-TOF-MS (m/z)=611.7807, theoretical molecular weight: 611.7810；Anal.Calcd for C40H25N3 (%): C 78.53, H 4.12, N 6.87, Found:C 78.52, H 4.14, N 6.86.
Embodiment 63
The target product in above formula, which is prepared, according to method identical with embodiment 47 (is compared to embodiment 47, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.74g, yield 85%.Matter Spectrometer MALDI-TOF-MS (m/z)=557.6424, theoretical molecular weight: 557.6420；Anal.Calcd for C32H19N3 (%): C 68.92, H 3.43, N 7.54, Found:C 68.92, H 3.44, N 7.55.
Embodiment 64
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.67g, yield 82%.Matter Spectrometer MALDI-TOF-MS (m/z)=569.7260, theoretical molecular weight: 569.7260；Anal.Calcd for C39H27N3 (%): C 82.22, H 4.78, N 7.38, Found:C 82.21, H 4.80, N 7.38.
Embodiment 65
The target product in above formula, which is prepared, according to method identical with embodiment 39 (is compared to embodiment 39, every a pair Answer the reactant of step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.63g, yield 84%.Matter Spectrometer MALDI-TOF-MS (m/z)=669.8465, theoretical molecular weight: 669.8460；Anal.Calcd for C47H31N3 (%): C 84.28, H 4.66, N 6.27, Found:C 84.28, H 4.65, N 6.27.
Embodiment 66
(1) in the there-necked flask of 500mL, the bromo- 9H- carbazole (39.37g, 160mmol) of investment 3-, naphthalene -2- ylboronic acid 250mL toluene is added in (19.51g, 160mmol), potassium carbonate (44.44g, 320mmol), under nitrogen atmosphere, is added four (three Phenylphosphine) palladium (0.37g, 0.32mmol), 50~150 DEG C of 4~48h of reaction are warming up to, liquid phase monitoring reaction is completed, and room is cooled to Temperature is washed, and 3- phenyl -9H- carbazole 32.70g, yield 84% can be obtained in filtering, pillar layer separation；
(2) in the there-necked flask of 500mL, 3- phenyl -9H- carbazole (14.60g, 60mmol), (4- bromophenyl) boric acid are put into (12.05g, 60mmol), sodium tert-butoxide (11.52g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.07g, 0.24mmol), 200mL toluene is added, under nitrogen atmosphere, is added palladium acetate (0.03g, 0.12mmol), is warming up to 50~150 DEG C 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filtering, (4- (3- can be obtained in pillar layer separation Phenyl -9H- carbazole -9- base) phenyl) boric acid 18.96g, yield 87%；
(3) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (1.99g, 10mmol), (4- (3- are put into Phenyl -9H- carbazole -9- base) phenyl) boric acid (7.26g, 20mmol), potassium carbonate (2.76g, 20mmol), addition 50mL toluene, 25mL ethyl alcohol and 25mL water are added tetrakis triphenylphosphine palladium (0.02g, 0.02mmol) under nitrogen atmosphere, it is warming up to 50~ 100 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, and filtering, pillar layer separation can be obtained final Product 5.84g, yield 81%.
Mass spectrograph MALDI-TOF-MS (m/z)=720.8944, theoretical molecular weight: 720.8940；Anal.Calcd for C50H32N4(%): C 83.31, H 4.47, N 7.77, Found:C 83.30, H 4.48, N 7.77.
Embodiment 67
By tin indium oxide (ITO) glass substrate in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, Zhi Houxian Continued to be cleaned by ultrasonic 15min with acetone and isopropanol afterwards, be dried in vacuo 2h (105 DEG C), at the UV ozone of followed by 15min Reason, is sent to vacuum evaporation plating machine for ito glass substrate.
By molybdenum trioxide (MoO3) vacuum deposition ito glass substrate up to 10nm thickness formed hole injection layer.
By N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines (NPB) vacuum deposition are infused in hole The thickness for entering layer up to 60nm forms hole transmission layer.
By (9H- carbazole -9- base) benzene (mCP) (as luminescent layer material of main part) of 1,3- bis- and 4,4 '-bis- (9- ethyl -3- Carbazole vinyl) -1, '-biphenyl (BCzVBi) (as luminescent layer guest materials) exists with the common vacuum deposition of the weight ratio of 95:5 Hole transmission layer forms luminescent layer up to the thickness of 20nm.
By 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) vacuum deposition on the light-emitting layer to 30nm's Thickness forms electron transport layer materials.
Lithium fluoride (LiF) vacuum deposition is formed into electron injecting layer to the thickness of 1nm on the electron transport layer.
Aluminium (Al) vacuum deposition is formed into cathode up to the thickness of 100nm in electron injecting layer.
The compound vacuum deposition that embodiment 36~65 is prepared is respectively adopted to be formed in cathode up to the thickness of 60nm Photosphere material out, to complete the preparation of organic illuminating element.Performance detection is carried out to the light-emitting component of preparation, Fig. 6~9 distinguishes It is special for B11 device and control group, wavelength-luminous intensity performance diagram of blank group device, voltage-current density-brightness Linearity curve figure, current density-current efficiency-power efficiency characteristic curve graph and brightness-external quantum efficiency characteristic curve graph, Figure 10 For wavelength-refractive index curve chart of B11 device and control group device.Specific detection data is shown in Table 2:
2 organic electroluminescence device performance characterization of table
Testing result shows what the compound being prepared using embodiment 36~65 was prepared as photosphere material out Light-emitting component current efficiency, power efficiency, external quantum efficiency and in terms of there is excellent performance, and be significantly better than pair According to group (device number D, using TPBi as electron transfer layer and out photosphere material simultaneously) and blank group (device number K).In addition, π bridge is attached with the site N relatively active in condensed hetero ring system, under the premise of reducing technology difficulty, is effectively extended point The length of son, improves the thermal stability of compound entirety, to effectively avoid destruction of the thermal accumlation to device architecture, effectively Improve the non-radiative degree of coupling and service life of device.
Embodiment 68
(1) in the there-necked flask of 500mL, bromobenzene (9.42g, 60mmol), aniline (11.18g, 120mmol), tertiary fourth are put into Sodium alkoxide (11.53g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol), are added the toluene of 250mL, in nitrogen Under atmosphere is enclosed, it is added tris(dibenzylideneacetone) dipalladium (0.29g, 0.3mmol), is warming up to 50~150 DEG C of 4~48h of reaction, liquid Mutually monitoring reaction is completed, and is cooled to 50 DEG C, and (4- bromophenyl) boric acid (12.05g, 60mmol), heating are added under nitrogen atmosphere To 50~150 DEG C of the reaction was continued 4~48h, liquid phase monitoring reaction is completed, and is cooled to room temperature, is washed, filtering, after filtrate concentration with Filter residue merges, and is recrystallized in ice bath with ethyl alcohol secondary, and (4- diphenylamino) boric acid 11.27g, yield 65% can be obtained；
(2) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), (4- hexichol are put into Amine phenyl) boric acid (8.67g, 30mmol), cesium carbonate (14.66g, 45mmol), 120mL toluene is added and adds under nitrogen atmosphere Enter [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.44g, 0.6mmol), be warming up to 50~100 DEG C reaction 4~ 48h, liquid phase monitoring reaction complete, be cooled to room temperature, wash, filter, concentration, pillar layer separation, can be obtained 4- (3- bromo- 1, 2,4- thiadiazoles -5- bases)-N, N- diphenylaniline 8.82g, yield 72%；
(3) in the there-necked flask of 250mL, 4- (bromo- 1,2,4- thiadiazoles -5- base of 3-)-N, N- diphenylaniline are put into 50mL toluene, 25mL second is added in (4.08g, 10mmol), phenyl boric acid (1.22g, 10mmol), potassium carbonate (2.76g, 20mmol) Pure and mild 25mL water is added tetrakis triphenylphosphine palladium (0.02g, 0.02mmol) under nitrogen atmosphere, is warming up to 50~100 DEG C instead 4~48h is answered, liquid phase monitoring reaction is completed, is cooled to room temperature, washes, final products can be obtained in filtering, pillar layer separation 3.60g, yield 89%.
Mass spectrograph MALDI-TOF-MS (m/z)=405.5186, theoretical molecular weight: 405.5190；Anal.Calcd for C26H19N3(%): C 77.01, H 4.72, N 10.36, Found:C 77.00, H 4.72, N 10.35.
Embodiment 69
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.00g, yield 86%. Mass spectrograph MALDI-TOF-MS (m/z)=581.7374, theoretical molecular weight: 581.7370；Anal.Calcd for C40H27N3 (%): C 82.59, H 4.68, N 7.22, Found:C 82.60, H 4.66, N 7.22.
Embodiment 70
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.74g, yield 86%. Mass spectrograph MALDI-TOF-MS (m/z)=551.7067, theoretical molecular weight: 551.7080；Anal.Calcd for C36H29N3 (%): C 78.37, H 5.30, N 7.62, Found:C 78.38, H 5.30, N 7.60.
Embodiment 71
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.31g, yield 84%. Mass spectrograph MALDI-TOF-MS (m/z)=631.7965, theoretical molecular weight: 631.7970；Anal.Calcd for C44H29N3 (%): C 83.65, H 4.63, N 6.65, Found:C 83.65, H 4.62, N 6.65.
Embodiment 72
(1) in the there-necked flask of 500mL, investment 2- bromodiphenylthiophene (15.79g, 60mmol), aniline (11.18g, 120mmol), sodium tert-butoxide (11.53g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol) are added The toluene of 250mL is added tris(dibenzylideneacetone) dipalladium (0.29g, 0.3mmol) under nitrogen atmosphere, it is warming up to 50~ 150 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to 50 DEG C, (3- bromophenyl) boric acid is added under nitrogen atmosphere (12.05g, 60mmol), is warming up to 50~150 DEG C the reaction was continued 4-48h, and liquid phase monitoring reaction is completed, is cooled to room temperature, water It washes, filters, merge after filtrate concentration with filter residue, recrystallized in ice bath with ethyl alcohol secondary, (3- (dibenzothiophenes-can be obtained 2- base (phenyl) amine) phenyl) boric acid 15.65g, yield 66%；
(2) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (1.99g, 10mmol), (3- (two are put into Benzothiophene -2- base (phenyl) amine) phenyl) boric acid (7.91g, 20mmol), potassium carbonate (2.76g, 20mmol), 50mL first is added Benzene, 25mL ethyl alcohol and 25mL water are added tetrakis triphenylphosphine palladium (0.02g, 0.02mmol) under nitrogen atmosphere, are warming up to 50 ~100 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to room temperature, wash, filtering, pillar layer separation can be obtained most Finished product 6.28g, yield 80%.
Mass spectrograph MALDI-TOF-MS (m/z)=785.0144, theoretical molecular weight: 785.0140；Anal.Calcd for C50H32N4(%): C 76.50, H 4.11, N 7.14, Found:C 76.50, H 4.10, N 7.15.
Embodiment 73
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.62g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=693.9535, theoretical molecular weight: 693.9530；Anal.Calcd for C48H43N3 (%): C 83.08, H 6.25, N 6.06, Found:C 83.08, H 6.26, N 6.07.
Embodiment 74
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.62g, yield 81%. Mass spectrograph MALDI-TOF-MS (m/z)=673.8786, theoretical molecular weight: 673.8780；Anal.Calcd for C47H35N3 (%): C 83.77, H 5.24, N 6.24, Found:C 83.76, H 5.24, N 6.25.
Embodiment 75
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.21g, yield 79%. Mass spectrograph MALDI-TOF-MS (m/z)=659.8106, theoretical molecular weight: 659.8110；Anal.Calcd for C44H29N5 (%): C 80.10, H 4.43, N 10.61, Found:C 80.09, H 4.44, N 10.60.
Embodiment 76
According to method identical with embodiment 72 prepare in above formula target compound (be compared to embodiment 72, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final products 4.58g, yield 80%.Mass spectrograph MALDI-TOF-MS (m/z)=572.7297, theoretical molecular weight: 572.7300；Anal.Calcd for C38H28N4(%): C 79.69, H 4.93, N 9.78, Found:C 79.68, H 4.95, N 9.78.
Embodiment 77
(1) in the there-necked flask of 500mL, bromobenzene (9.42g, 60mmol), aniline (11.18g, 120mmol), tertiary fourth are put into Sodium alkoxide (11.53g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol), are added the toluene of 250mL, in nitrogen Under atmosphere is enclosed, it is added tris(dibenzylideneacetone) dipalladium (0.29g, 0.3mmol), is warming up to 80~150 DEG C of 4~48h of reaction, liquid Mutually monitoring reaction is completed, and is cooled to 50 DEG C, and (4- bromophenyl) boric acid (12.05g, 60mmol), heating are added under nitrogen atmosphere To 80~150 DEG C of the reaction was continued 4~48h, liquid phase monitoring reaction is completed, and is cooled to room temperature, is washed, filtering, after filtrate concentration with Filter residue merges, and is recrystallized in ice bath with ethyl alcohol secondary, and (4- diphenylamino) boric acid 11.27g, yield 65% can be obtained；
(2) in the there-necked flask of 250mL, the bromo- 5- of 3- chloro- 1,2,4- thiadiazoles (5.98g, 30mmol), (4- hexichol are put into Amine phenyl) boric acid (8.67g, 30mmol), cesium carbonate (14.66g, 45mmol), 120mL toluene is added and adds under nitrogen atmosphere Enter [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride (0.44g, 0.6mmol), be warming up to 50~100 DEG C reaction 4~ 48h, liquid phase monitoring reaction complete, be cooled to room temperature, wash, filter, concentration, pillar layer separation, can be obtained 4- (3- bromo- 1, 2,4- thiadiazoles -5- bases)-N, N- diphenylaniline 8.82g, yield 72%；
(3) in the there-necked flask of 500mL, investment 4- bromodiphenylthiophene (15.79g, 60mmol), aniline (11.18g, 120mmol), sodium tert-butoxide (11.53g, 120mmol), tri-tert-butylphosphine tetrafluoroborate (0.15g, 0.6mmol) are added The toluene of 250mL is added tris(dibenzylideneacetone) dipalladium (0.29g, 0.3mmol) under nitrogen atmosphere, it is warming up to 80~ 150 DEG C of 4~48h of reaction, liquid phase monitoring reaction are completed, are cooled to 50 DEG C, (4- bromophenyl) boric acid is added under nitrogen atmosphere (12.05g, 60mmol), is warming up to 80~150 DEG C the reaction was continued 4~48h, and liquid phase monitoring reaction is completed, is cooled to room temperature, water It washes, filters, merge after filtrate concentration with filter residue, recrystallized in ice bath with ethyl alcohol secondary, (4- (dibenzothiophenes-can be obtained 4- base (phenyl) amine) phenyl) boric acid 16.12g, yield 68%；
(4) in the there-necked flask of 250mL, 4- (bromo- 1,2,4- thiadiazoles -5- base of 3-)-N, N- diphenylaniline are put into (4.08g, 10mmol), (4- (dibenzothiophenes -4- base (phenyl) amine) phenyl) boric acid (3.95g, 10mmol), potassium carbonate 50mL toluene, 25mL ethyl alcohol and 25mL water is added in (2.76g, 20mmol), under nitrogen atmosphere, tetrakis triphenylphosphine palladium is added (0.02g, 0.02mmol) is warming up to 50~100 DEG C of 4~48h of reaction, and liquid phase monitoring reaction is completed, is cooled to room temperature, washes, Final products 5.43g, yield 80% can be obtained in filtering, pillar layer separation.
Mass spectrograph MALDI-TOF-MS (m/z)=678.8725, theoretical molecular weight: 678.8720；Anal.Calcd for C44H30N4(%): C 77.85, H 4.45, N 8.25, Found:C 77.85, H 4.47, N 8.24.
Embodiment 78
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.71g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=567.7687, theoretical molecular weight: 567.7690；Anal.Calcd for C36H29N3 (%): C 76.16, H 5.15, N 7.40, Found:C 76.16, H 5.17, N 7.40.
Embodiment 79
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.30g, yield 84%. Mass spectrograph MALDI-TOF-MS (m/z)=631.7976, theoretical molecular weight: 631.7970；Anal.Calcd for C44H29N3 (%): C 83.65, H 4.63, N 6.65, Found:C 83.64, H 4.65, N 6.65.
Embodiment 80
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.76g, yield 80%. Mass spectrograph MALDI-TOF-MS (m/z)=595.7204, theoretical molecular weight: 595.7200；Anal.Calcd for C40H25N3 (%): C 80.65, H 4.23, N 7.05, Found:C 80.66, H 4.22, N 7.05.
Embodiment 81
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.88g, yield 83%. Mass spectrograph MALDI-TOF-MS (m/z)=587.7590, theoretical molecular weight: 587.7590；Anal.Calcd for C38H25N3 (%): C 77.65, H 4.29, N 7.15, Found:C 77.65, H 4.30, N 7.16.
Embodiment 82
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 4.93g, yield 86%. Mass spectrograph MALDI-TOF-MS (m/z)=573.8432, theoretical molecular weight: 573.8430；Anal.Calcd for C38H43N3 (%): C 79.54, H 7.55, N 7.32, Found:C 79.55, H 7.55, N 7.30.
Embodiment 83
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.02g, yield 82%. Mass spectrograph MALDI-TOF-MS (m/z)=611.7815, theoretical molecular weight: 611.7810；Anal.Calcd for C40H25N3 (%): C 78.53, H 4.12, N 6.87, Found:C 79.55, H 7.55, N 7.30.
Embodiment 84
According to method identical with embodiment 68 prepare in above formula target compound (be compared to embodiment 68, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.10g, yield 80%. Mass spectrograph MALDI-TOF-MS (m/z)=637.8450, theoretical molecular weight: 637.8450；Anal.Calcd for C44H35N3 (%): C 82.85, H 5.53, N 6.59, Found:C 82.86, H 5.53, N 6.60.
Embodiment 85
According to method identical with embodiment 72 prepare in above formula target compound (be compared to embodiment 72, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 6.03g, yield 78%. Mass spectrograph MALDI-TOF-MS (m/z)=772.9703, theoretical molecular weight: 772.9700；Anal.Calcd for C54H36N4 (%): C 83.91, H 4.69, N 7.25, Found:C 83.90, H 4.69, N 7.25.
Embodiment 86
According to method identical with embodiment 72 prepare in above formula target compound (be compared to embodiment 72, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 6.96g, yield 79%. Mass spectrograph MALDI-TOF-MS (m/z)=881.0736, theoretical molecular weight: 881.0740；Anal.Calcd for C58H40N8 (%): C 79.07, H 4.58, N 12.72, Found:C 79.06, H 4.59, N 12.71.
Embodiment 87
According to method identical with embodiment 77 prepare in above formula target compound (be compared to embodiment 77, it is each The reactant of corresponding step can be different, but reactant molar ratio, reaction condition are identical), obtain final product 5.76g, yield 77%. Mass spectrograph MALDI-TOF-MS (m/z)=748.9484, theoretical molecular weight: 748.9480；Anal.Calcd for C52H36N4 (%): C 83.39, H 4.85, N 7.48, Found:C 83.40, H 4.85, N 7.47.
Embodiment 88
By tin indium oxide (ITO) glass substrate in succession in cleaning agent and deionized water with ultrasonic cleaning 1h, Zhi Houxian Continued to be cleaned by ultrasonic 15min with acetone and isopropanol afterwards, be dried in vacuo 2h (105 DEG C), at the UV ozone of followed by 15min Reason, is sent to vacuum evaporation plating machine for ito glass substrate.
By molybdenum trioxide (MoO3) vacuum deposition ito glass substrate up to 10nm thickness formed hole injection layer.
By N, N '-diphenyl-N, N '-(1- naphthalene) -1,1 '-biphenyl -4,4 '-diamines (NPB) vacuum deposition are infused in hole The thickness for entering layer up to 60nm forms hole transmission layer.
By (9H- carbazole -9- base) benzene (mCP) (as luminescent layer material of main part) of 1,3- bis- and BCzVBi (as luminescent layer Guest materials) with the common vacuum deposition of the weight ratio of 95:5 on the hole transport layer to 20nm thickness formed luminescent layer.
By 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) vacuum deposition on the light-emitting layer to 30nm's Thickness forms electron transport layer materials.
Lithium fluoride (LiF) vacuum deposition is formed into electron injecting layer to the thickness of 1nm on the electron transport layer.
Aluminium (Al) vacuum deposition is formed into cathode up to the thickness of 100nm in electron injecting layer.
The compound vacuum deposition that embodiment 68~87 is prepared is respectively adopted to be formed in cathode up to the thickness of 60nm Photosphere material out, to complete the preparation of organic illuminating element.Performance detection, Figure 11~14 point are carried out to the light-emitting component of preparation It Wei not C5 device and control group, wavelength-luminous intensity performance diagram of blank group device, voltage-current density-brightness spy Linearity curve figure, current density-current efficiency-power efficiency characteristic curve graph and brightness-external quantum efficiency characteristic curve graph, Figure 15 For wavelength-refractive index curve chart of C5 device and control group device.Specific detection data is shown in Table 3:
3 organic electroluminescence device performance characterization of table
Testing result shows using use 68~87 compound of embodiment as the luminous member that photosphere material is prepared out Part current efficiency, power efficiency, external quantum efficiency and in terms of there is excellent performance, and be significantly better than control group (device number D, using TPBi as electron transfer layer and out photosphere material simultaneously) and blank group (device number K).Arylamine group Introducing, improve the thermal stability of molecule entirety, effectively avoid light be converted into thermal accumlation caused by heat to device lifetime with And the influence of stability.In addition, compound entirety cross arrangement forms dense accumulation structure, the 1 of core, 2,4- thiadiazoles groups It is regular to the progress of intermolecular oriented, the refractive index and extinction coefficient of compound entirety under stacking states are improved, thus Device optical coupling output efficiency is further promoted, improves device in current efficiency, power efficiency, external quantum efficiency and coloration etc. The comprehensive performance of aspect.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned Embodiment is changed, modifies, replacement and variant.

Claims (10)

1. a kind of compound, which is characterized in that the compound is structure shown in formula (I),
Wherein,
R1And R2Separately it is hydrogen, cyano, nitro, amidino groups, sulfonyl, the sulfinat optionally replaced, optionally replaces C1~20Alkyl, the amino optionally replaced, the amino optionally replaced, the C optionally replaced1~20Miscellaneous alkyl, the C optionally replaced1~20Silicon Alkyl, the C optionally replaced6~30Aryl, the C optionally replaced3~30Heteroaryl, the C optionally replaced6~30Aryloxy group optionally replaces C6~30Arylthio, the C optionally replaced6~30Aryl amine or the C optionally replaced2~30Heterocycle；
L1And L2The separately C optionally to replace6~30Aryl or the C optionally replaced3~30Heteroaryl, d and e are separately It is 0 or 1, and d and e are not 0 simultaneously.
2. compound according to claim 1, which is characterized in that
R1And R2At least one of beWherein, Ar is The C optionally replaced6~50Aryl, the C optionally replaced3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Virtue Sulfenyl, the C optionally replaced6~50Aryl amine or the C optionally replaced2~50Heterocycle；A is the C optionally replaced1~20Alkyl, optionally Substituted amino, the C optionally replaced6~50Aryl, the C optionally replaced3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, optionally Substituted C6~50Arylthio, the C optionally replaced6~50Aryl amine or the C optionally replaced2~50Heterocycle；Each X is separately C, the N or each X optionally replaced is separately C, the N optionally replaced and the two adjacent X and C optionally replaced6~50Virtue Base, the C optionally replaced3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Arylthio optionally replaces C6~50Aryl amine and the C optionally replaced2~50At least one of heterocycle is formed and ring；Y1And Y2It is separately optionally to take C, N, O or the S in generation, f are 0 or 1；A1And A2The separately C optionally to replace1~20Miscellaneous alkyl, the C optionally replaced6~50Virtue Base, the amino optionally replaced, the C optionally replaced3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Virtue Sulfenyl, the C optionally replaced6~50Aryl amine or the C optionally replaced2~50Heterocycle.
3. compound according to claim 1 or 2, which is characterized in that
R1And R2At least one of be following subformula:
Wherein, R3、R4、R5、R6、R7And R8The separately C optionally to replace1~20Alkyl, the ammonia optionally replaced Base, the C optionally replaced1~50Miscellaneous alkyl, the C optionally replaced1~20Silylation, the C optionally replaced6~50Aryl optionally replaces C3~50Heteroaryl, the C optionally replaced6~50Aryloxy group, the C optionally replaced6~50Arylthio, the C optionally replaced6~50Aryl amine or The C optionally replaced2~50Heterocycle, X are Y defined by claim 21And Y2Separately for C, N, O for optionally replacing or S；
A1And A2At least one of beWherein, Ar, A and X are defined by claim 2.
4. compound according to claim 1, which is characterized in that
R1And R2At least one of be following subformula:
5. compound according to claim 1, which is characterized in that the compound has the structure of one of:
6. a kind of method for preparing the described in any item compounds of Claims 1 to 5 characterized by comprising
The contact of compound shown in compound shown in compound, formula (b) shown in formula (a) and formula (c), to obtain claim 1 ~5 described in any item compounds,
Wherein, Z1And Z2It is separately Cl or Br, R1And R2For defined by any one of Claims 1 to 4, L1、L2, d and e For defined by claim 1.
7. according to the method described in claim 6, it is characterized in that, the contact is there are the mixing of palladium catalyst and alkali is molten It is carried out in agent.
8. the method according to the description of claim 7 is characterized in that the palladium catalyst is [1,1 '-bis- (diphenylphosphinos) two At least one of luxuriant iron] palladium chloride, tetra-triphenylphosphine palladium, tris(dibenzylideneacetone) dipalladium and palladium acetate；
Optionally, the alkali is cesium carbonate, cesium fluoride, potassium fluoride, potassium carbonate, potassium phosphate, lithium phosphate, sodium carbonate, four fourths of fluorination At least one of base ammonium and sodium tert-butoxide；
Optionally, the mixed solvent includes toluene, dimethylbenzene, ethyl alcohol, n,N-Dimethylformamide, n,N-dimethylacetamide At least one of with water.
9. a kind of electronic component characterized by comprising go out photosphere, cathode and anode, wherein the photosphere out is formed in institute A side surface of the cathode far from the anode is stated, the photosphere out is formed by the described in any item compounds of Claims 1 to 5.
10. electronic component according to claim 9, which is characterized in that it is described go out photosphere with a thickness of 1~100nm.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467561A (en) * 2018-11-19 2019-03-15 广东工业大学 A kind of double donor hole mobile materials containing phenothiazine structure and preparation method thereof and perovskite solar battery
CN110016046A (en) * 2019-04-24 2019-07-16 武汉华星光电半导体显示技术有限公司 Electroluminescent material, the preparation method of electroluminescent material and luminescent device
CN110156611A (en) * 2019-05-23 2019-08-23 武汉尚赛光电科技有限公司 A kind of phenyl cladodification luminescent material and its organic electroluminescence device
CN113121519A (en) * 2021-04-13 2021-07-16 吉林奥来德光电材料股份有限公司 Arylamine compound and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103588770A (en) * 2013-11-27 2014-02-19 武汉尚赛光电科技有限公司 1,2,4-thiadiazole derivatives and their use as electroluminescent materials
WO2014192681A1 (en) * 2013-05-31 2014-12-04 コニカミノルタ株式会社 Resin composition, optical member, optical film, polarizing plate, circular polarizing plate, and image display device

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8314119B2 (en) * 2006-11-06 2012-11-20 Abbvie Inc. Azaadamantane derivatives and methods of use
CN106661001A (en) * 2014-05-14 2017-05-10 哈佛学院院长等 Organic light-emitting diode materials
JP6372317B2 (en) * 2014-11-14 2018-08-15 宇部興産株式会社 Thermoelectric conversion material containing benzobis (thiadiazole) derivative and thermoelectric conversion element using the same
CN109438435B (en) * 2018-09-27 2021-08-06 武汉尚赛光电科技有限公司 1,2, 4-thiadiazole compound and preparation method and application thereof
CN109369567B (en) * 2018-09-27 2021-03-02 武汉尚赛光电科技有限公司 1,2, 4-thiadiazole compound and preparation method and application thereof
CN109232475B (en) * 2018-09-27 2021-06-01 武汉尚赛光电科技有限公司 1,2, 4-thiadiazole compound and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014192681A1 (en) * 2013-05-31 2014-12-04 コニカミノルタ株式会社 Resin composition, optical member, optical film, polarizing plate, circular polarizing plate, and image display device
CN103588770A (en) * 2013-11-27 2014-02-19 武汉尚赛光电科技有限公司 1,2,4-thiadiazole derivatives and their use as electroluminescent materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WENZHI ZHANG ET AL.: "Towards highly efficient thermally activated delayed fluorescence devices through a trap-assisted recombination mechanism and reduced interfacial exciton annihilation", 《JOURNAL OF MATERIALS CHEMISTRY C》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467561A (en) * 2018-11-19 2019-03-15 广东工业大学 A kind of double donor hole mobile materials containing phenothiazine structure and preparation method thereof and perovskite solar battery
CN109467561B (en) * 2018-11-19 2021-07-02 广东工业大学 Double-donor hole transport material containing phenothiazine structure, preparation method thereof and perovskite solar cell
CN110016046A (en) * 2019-04-24 2019-07-16 武汉华星光电半导体显示技术有限公司 Electroluminescent material, the preparation method of electroluminescent material and luminescent device
CN110156611A (en) * 2019-05-23 2019-08-23 武汉尚赛光电科技有限公司 A kind of phenyl cladodification luminescent material and its organic electroluminescence device
CN110156611B (en) * 2019-05-23 2022-11-11 武汉尚赛光电科技有限公司 Phenyl branched luminescent material and organic electroluminescent device thereof
CN113121519A (en) * 2021-04-13 2021-07-16 吉林奥来德光电材料股份有限公司 Arylamine compound and preparation method and application thereof

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