CN104327837A - Organic electroluminescent semiconductor material and preparation method and application thereof - Google Patents
Organic electroluminescent semiconductor material and preparation method and application thereof Download PDFInfo
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- CN104327837A CN104327837A CN201310309638.9A CN201310309638A CN104327837A CN 104327837 A CN104327837 A CN 104327837A CN 201310309638 A CN201310309638 A CN 201310309638A CN 104327837 A CN104327837 A CN 104327837A
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- 0 *[Si](*)(c1c-2[s]c(I)c1)c1c-2[s]c(I)c1 Chemical compound *[Si](*)(c1c-2[s]c(I)c1)c1c-2[s]c(I)c1 0.000 description 1
- RXDXFOZUFLJQFE-UHFFFAOYSA-N CC1(C)OB(c2cc3nccnc3cc2)OC1 Chemical compound CC1(C)OB(c2cc3nccnc3cc2)OC1 RXDXFOZUFLJQFE-UHFFFAOYSA-N 0.000 description 1
- ZYWICCYXTGRUNM-UHFFFAOYSA-N CC1(C)OB(c2cc3nccnc3cc2)OC1(C)C Chemical compound CC1(C)OB(c2cc3nccnc3cc2)OC1(C)C ZYWICCYXTGRUNM-UHFFFAOYSA-N 0.000 description 1
- PFFJVUAESGNBCQ-UHFFFAOYSA-N CCCCCC[Si+](C)(c1c-2[s]c(I)c1)c1c-2[s]c(I)c1 Chemical compound CCCCCC[Si+](C)(c1c-2[s]c(I)c1)c1c-2[s]c(I)c1 PFFJVUAESGNBCQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an organic electroluminescent semiconductor material and a preparation method and application thereof, the organic electroluminescent semiconductor material has the molecular structural formula as shown in (I), wherein R is phenyl or C1-C6 alkyl. The preparation method includes the step of providing a compound A and a compound B for Suzuki coupling reaction of the compound A and the compound B to prepare the organic electroluminescent semiconductor material, the organic electroluminescent semiconductor material has excellent thermal stability, and the film recrystallization or melting phenomenon can be avoided. At the same time, the organic electroluminescent semiconductor material has excellent charge carrier transport properties and solubility, good film-forming property, and wide application range. The preparation method is mature in process and high in yield.
Description
Technical field
The invention belongs to technical field of organic luminescence materials, relate to a kind of organic electroluminescent semiconductor material and its preparation method and application specifically.
Background technology
Organic electroluminescence device (Organic Light Emission Diode, hereinafter referred to as OLED) is a kind of current mode light emitting semiconductor device based on organic materials.Under the principle of luminosity of OLED is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by transmission ofenergy to luminescent material, and excitation electron is from ground state transition to excited state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
OLED has that luminous efficiency is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, the advantage such as light, thin, have high-resolution, wide viewing angle, fast response time, low cost and the advantage such as bright in luster simultaneously, a kind of technique of display and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, therefore, thought to be most likely at the device of new generation following illumination and display device market occupying dominance by insider.Just because of this OLED, there is this advantage, along with the development of information age, there is the concern that the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating are more and more subject to people, higher requirement is proposed to the material of preparation OLED simultaneously.
1987, Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.But realize the application purpose such as total colouring and illumination, luminescent device must have certain efficiency and life-span.And due to the normally few son of electronics in organic materials transferring charge, when being applied in electroluminescent device, during as being applied in OLED, have impact on OLED light rate.In addition, the electroluminescent organic material having better electronic transmission performance at present also compares shortage.
At present, simple bithiophene thiophene coughs up blue light-emitting, and because σ *-π * conjugation reduces its LUMO level, therefore cough up also can as the electron transport material of multilayer organic electroluminescence device for this bithiophene thiophene.But, in actual application, find that this bithiophene thiophene coughs up formed thin film layer thermally labile, be applied to device, usually can cause the sharply reduction of device performance because of crystallization or fusing.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of organic electroluminescent semiconductor material is provided, cough up to solve existing simple bithiophene thiophene the technical problem that poor heat stability crystallization easily occurs or melts unfavorable phenomenon.
Another object of the present invention is to provide a kind of productive rate high, the preparation method of the organic electroluminescent semiconductor material be easy to operate and control.
Further aim of the present invention is the application providing above-mentioned organic electroluminescent semiconductor material.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic electroluminescent semiconductor material, its general formula of molecular structure is following (I):
In formula, R is phenyl or C
1~ C
6alkyl.
And a kind of method preparing above-mentioned organic electroluminescent semiconductor material, comprises the steps:
Compd A, the B of following structural formula general formula are provided:
In anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, described compd A and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Wherein, the R in compd A, general structure (I) is phenyl or C
1~ C
6alkyl.
And, above-mentioned organic electroluminescent semiconductor material at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.
Above-mentioned organic electroluminescent semiconductor material introduces quinoxaline group by coughing up on group at bithiophene thiophene, because this quinoxaline group has certain rigidity and steric hindrance, thus gives the thermal stability of this organic electroluminescent semiconductor material excellence.Simultaneously, cough up group due to bithiophene thiophene and there is lower LUMO level and larger coplanarity, itself there is extraordinary electronic transmission performance, quinoxaline group again owing to introducing has lower LUMO level and larger coplanarity equally, thus there is excellent electronic transmission performance, therefore, this quinoxaline group and bithiophene thiophene are coughed up group and are acted synergistically, and give the electronic transmission performance of this organic electroluminescent semiconductor material excellence.In addition, organic electroluminescent semiconductor material also has excellent solvability and film-forming properties.Just because of this organic electroluminescent semiconductor material, there is the excellent performance such as thermostability, carrier transport, widened the range of application of this organic electroluminescent semiconductor material.
Above-mentioned organic electroluminescent method for preparing semi-conducting material adopts ripe Suzuki linked reaction, compd A and B are carried out coupling, thus makes the productive rate of target product high, and its linked reaction is easy to operate and control, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the schema of embodiment of the present invention organic electroluminescent method for preparing semi-conducting material;
The OLED structure schematic diagram that Fig. 2 utilizes embodiment of the present invention organic electroluminescent semiconductor material to prepare;
In Fig. 3 Application Example 4, the OLED of preparation carries out spectroscopic analysis figure when 4.5V.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of organic electroluminescent semiconductor material with superior heat-stability and electronic transmission performance.The general formula of molecular structure of this organic electroluminescent semiconductor material is following (I):
Particularly, the R in logical formula I formula is phenyl or C
1~ C
6alkyl.Wherein, the carrier transmission performance that can strengthen organic electroluminescent semiconductor material excellence that this R group exists and luminous efficiency, can improve the solvability of this organic electroluminescent semiconductor material simultaneously, is conducive to improving the film forming properties in the course of processing.Accordingly, in a preferred embodiment, this R group is phenyl or C
3~ C
6alkyl.
In a particular embodiment, the R in logical formula I formula is C
1~ C
6alkyl time, this R can be the groups such as methyl, propyl group and hexyl.
Like this, in above-mentioned organic electroluminescent semiconductor material, bithiophene thiophene coughs up the three-ring system of β position by Siliciumatom bridging that group is two bithiophenes two thiphene ring, compared with the coupling aromatic compound that other are general, it has lower LUMO energy level, has larger coplanarity simultaneously.Therefore, bithiophene thiophene is coughed up group and is had extraordinary electronic transmission performance.In above-mentioned organic electroluminescent semiconductor material, quinoxaline group has lower LUMO level and larger coplanarity equally, thus has excellent electronic transmission performance.Therefore, this quinoxaline group and bithiophene thiophene are coughed up group and are acted synergistically, and give the electronic transmission performance that this organic electroluminescent semiconductor material is more excellent.In addition, because this quinoxaline group has certain rigidity and steric hindrance, thus give the thermal stability of this organic electroluminescent semiconductor material excellence, efficiently solve existing bithiophene thiophene and cough up the low and technical problem of the easy crystallization of thin film layer that is that cause it to be formed or fusing of compound thermostability.Particularly, the thermostability of this organic electroluminescent semiconductor material refers to hereafter table 1.The introducing of R group, increases the sterically hindered of molecule on the one hand, Organic Electron Transport Material crystallinity is suppressed, improves its film forming properties; On the other hand, the aliphatic chain in R group effectively improves Organic Electron Transport Material solvability.By the selection of the R in mutual-through type (I) formula, dissolving and the film forming properties of this organic electroluminescent semiconductor material can be improved further.
Correspondingly, the embodiment of the present invention additionally provides the method that one prepares the organic electroluminescent semiconductor material of above-mentioned general formula of molecular structure (I), and its preparation method flow process as shown in Figure 1.This organic electroluminescent method for preparing semi-conducting material comprises the steps:
S01., compd A, the B of following structural formula general formula are provided:
S02. compd A, B are carried out Suzuki linked reaction and generate organic electroluminescent semiconductor material: in anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, compd A in step S01 and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Particularly, in above-mentioned steps S01, be phenyl or C about the R in compd A molecular structural formula
1~ C
6alkyl, this R is preferably phenyl or C
3~ C
6alkyl, be more preferably phenyl.In addition, compd A, compd B can be directly commercial or according to the record of document or prepare according to organic chemical reactions principle.
In above-mentioned steps S02, the Suzuki coupled reaction chemical formula between compd A, B is as follows:
In this Suzuki coupled reaction, the condition of this Suzuki coupled reaction can directly be arranged according to the condition of the Suzuki coupled reaction of existing routine, in the present invention in order to improve the Suzuki coupled reaction speed between compd A, B, improve the productive rate of organic electroluminescent semiconductor material, in a preferred embodiment, the condition setting of this Suzuki coupled reaction is: the temperature of Suzuki linked reaction is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours.
In step S02, the consumption of reactant compound A, B can directly add according to ratio in both chemical equation.In the present invention, carry out to forward to impel the Suzuki linked reaction between compd A, B, improve Suzuki coupled reaction speed, improve the productive rate of organic electroluminescent semiconductor material, in a preferred embodiment, the mol ratio of reactant compound A, B consumption is 1:(2 ~ 3).
In step S02, organo-metallic catalyst is preferably organic palladium catalyzer, in further preferred embodiment, this organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium.
In step S02, as preferred embodiment, the consumption of this organo-metallic catalyst and the mol ratio of compd A consumption are (0.05 ~ 0.1): 1.
As further preferred embodiment, organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium, and the mol ratio of the consumption of organic palladium catalyzer and compd A consumption is (0.05 ~ 0.1): 1.
The catalyzer of above-mentioned preferred kind and consumption can provide Suzuki linked reaction speed, improve the productive rate of embodiment of the present invention target product, certainly the condition of Suzuki linked reaction can also be reduced, as made above-mentioned organic electroluminescent method for preparing semi-conducting material embodiment Suzuki linked reaction can be 75 ~ 120 DEG C in temperature, the reaction times be carry out smoothly under condition for 24 ~ 48 hours.
By above-mentioned, in above-mentioned organic electroluminescent method for preparing semi-conducting material embodiment, the Suzuki linked reaction condition between reactant compound A, B can be at least following preferred implementation:
As a preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is organic palladium catalyzer.
As another preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is the organic palladium catalyzer of tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium.
As another preferred embodiment, the mol ratio of compd A, B consumption is 1:(2 ~ 3); The Suzuki linked reaction temperature of compd A, B is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours; Organo-metallic catalyst is the organic palladium catalyzer of tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium, while the mol ratio of the consumption of organic palladium catalyzer and compd A consumption is (0.05 ~ 0.1): 1.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, Suzuki linked reaction need be carried out in the presence of alkali, in Suzuki linked reaction, the power of alkali (negative ion) is not only depended in the impact of alkali, and cationic character will be taken into account, if positively charged ion too little being unfavorable for generates middle transition state ylide (Pd) intermediate, the speed that conductively-closed is reacted when positively charged ion is too little and efficiency will significantly decline, suitably large cationic alkali, can accelerate the speed of Suzuki reaction.Therefore, in the present invention, this alkali Cs
2cO
3, K
2cO
3, Na
2cO
3in one or more mixture, its addition is 8 ~ 12 times of compd A mole dosage.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, Suzuki linked reaction must be reacted in oxygen-free environment, this is because the organo-metallic catalyst of Suzuki reaction is all be afraid of oxygen, if the existence of aerobic in reaction system, can catalyst deactivation be caused, thus cause Suzuki coupling reaction to carry out.Oxygen-free environment in reaction system can adopt vacuum or be full of rare gas element to realize, and is preferably full of rare gas element to realize oxygen-free environment, and this rare gas element is the rare gas element that the art is commonly used, such as nitrogen, argon gas etc., preferred nitrogen.
In this step S02, in each embodiment of above-mentioned organic electroluminescent method for preparing semi-conducting material, the reaction solvent of Suzuki linked reaction directly can select the solvent of Suzuki linked reaction routine.As preferred embodiment, the solvent of above-mentioned Suzuki linked reaction is organic solvent.Particularly, this organic solvent is the double solvents of any one or more in tetrahydrofuran (THF), glycol dimethyl ether, toluene.This preferred solvent can effectively dissolve each reactive component, thus improves the above-mentioned speed of reaction of Suzuki linked reaction and the yield of target product.
After Suzuki linked reaction in above-mentioned steps S02, generation such as above-mentioned general structure is the organic electroluminescent semiconductor material of (I).In this general structure (I), R is phenyl or C
1~ C
6alkyl, R is preferably phenyl or C
3~ C
6alkyl, be more preferably phenyl group.That is, the R group in this general structure (I) in R group and above-mentioned steps S01 in compd A molecular structure is one to one.
In addition, in the nature of things, as other organic syntheses, the purification step of the organic electroluminescent semiconductor material to general structure (I) is also comprised.This purification step preferably carries out as follows: pour in saturated aqueous ammonium chloride by the reaction solution of gained after Suzuki linked reaction, with dichloromethane extraction, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, subsequently crude product is carried out silica gel column chromatography separating-purifying, finally obtain pure organic electroluminescent semiconductor material.
By above-mentioned, above-mentioned organic electroluminescent method for preparing semi-conducting material adopts ripe Suzuki linked reaction, compd A and B are carried out coupling, thus make the productive rate of target product high, and its linked reaction is easy to operate and control, without the need to special equipment and environmental requirement, its preparation method technique is simple, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
Correspondingly, the embodiment of the present invention additionally provides the Application Areas of organic electroluminescent semiconductor material mentioned above.Have as the thermostability of above-mentioned excellence, carrier transport, solvability and film forming properties just because of organic electroluminescent semiconductor material mentioned above, the thermal stability of its excellence can avoid its film recrystallization phenomenon to occur, and excellent carrier transmission performance improves the luminous efficiency of organic electroluminescent semiconductor material.Therefore, this organic electroluminescent semiconductor material can at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.As in application process, using this organic electroluminescent semiconductor material as blue-ray organic electroluminescent material.
In concrete Application Example, this organic electroluminescent semiconductor material is utilized to prepare as organic electroluminescence device.As shown in Figure 2, it comprises anode layer 1, organic function layer 2, cathode layer 3 to this organic electroluminescence device structure.Wherein, organic function layer 2 comprises the hole transmission layer 21, luminescent layer 22 and the electron transfer layer 23 that stack gradually, and electron transfer layer 23 and the stacked combination of cathode layer 3, hole transmission layer 21 and the stacked combination of anode layer 1, luminescent layer 22 material is organic electroluminescent semiconductor material mentioned above.In addition, anode layer 1, cathode layer 3, hole transmission layer 21, electron transfer layer 23 layers of material material that this area all can be selected conventional.The thickness of each layer also can be arranged according to the thickness of this area routine.
Certainly, as the advantageous applications embodiment of this organic electroluminescent semiconductor material, this organic function layer 2 can also comprise hole injection layer and electron injecting layer (figure does not show), or comprises electronic barrier layer, hole blocking layer (figure does not show) further.This hole injection layer preferably contained, electron injecting layer, electronic barrier layer, hole blocking layer each layer lamination order are carried out stacked according to the structure of this area organic electroluminescence device routine, do not specially require in the present invention.
Certainly, as the advantageous applications embodiment of this organic electroluminescent semiconductor material, organic electroluminescence device also comprises substrate (figure do not show), and this substrate can be bonded inversion organic electroluminescence device with cathode layer 3 outside surface is stacked, or with the stacked combination of anode layer 1 outside surface.
In addition, if be not identical group by two R settings in organic electroluminescent semiconductor material general formula of molecular structure (I) mentioned above simultaneously, and this group is phenyl or C
1~ C
6alkyl or C
6during above alkyl, also in scope disclosed by the invention.This can be prepared by the compd A set in organic electroluminescent method for preparing semi-conducting material mentioned above the organic electroluminescent semiconductor material that R group changes.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
A kind of organic electroluminescent semiconductor material 5,5 '-two (quinoxalin-6-yl)-1,1 '-dimethyl two bithiophene thiophene coughed up containing thiophene is coughed up (called after DQDTMSi), and its molecular structural formula is as following I
1shown in:
This organic electroluminescent semiconductor material I
1preparation method comprise the steps:
(1) compd A (5,5 '-two iodo-1,1 '-dimethyl two bithiophene thiophene is coughed up) providing following structural formula to represent respectively and compd B (6-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) quinoxaline),
(2) by compd A (5,5 '-two iodo-1,1 '-dimethyl two bithiophene thiophene is coughed up) 5.0mmol, B(6-(4,4,5, 5-tetramethyl--1, 3,2-dioxaborolanes-2-base) quinoxaline) 10.0mmol, catalyzer (tetrakis triphenylphosphine palladium) 0.02mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the Na of tetrahydrofuran solution 65mL, 2mol/L
2cO
3aqueous solution 35ml, Suzuki coupling reaction is carried out in mixed solution heating, 75 ~ 80 DEG C of back flow reaction 48h, the obtained organic semiconductor material 5 coughed up containing thiophene containing P1, 5 '-two (quinoxalin-6-yl)-1, the reaction solution that 1 '-dimethyl two bithiophene thiophene is coughed up, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the solid product 5 after purifying, 5 '-two (quinoxalin-6-yl)-1, 1 '-dimethyl two bithiophene thiophene is coughed up.The productive rate that this 5,5 '-two (quinoxalin-6-yl)-1,1 '-dimethyl two bithiophene thiophene is coughed up is 59%.
5,5 '-two (quinoxalin-6-yl)-1,1 '-dimethyl two bithiophene thiophene prepared by the present embodiment 1 is coughed up compound and carries out mass spectroscopy and ultimate analysis, analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z479 (M
+);
Ultimate analysis: C
26h
18n
4s
2si, C, 65.20; H, 3.84; N, 11.75.
Embodiment 2:
Organic electroluminescent semiconductor material 5,5 '-two (quinoxalin-6-yl)-1,1 '-dipropyl two bithiophene thiophene that a kind of thiophene is coughed up is coughed up (called after DQDTPSi), and its molecular structural formula is as shown in following I 2:
This organic electroluminescent semiconductor material I
2preparation method comprise the steps:
(1) compd A (5,5 '-two iodo-1,1 '-dipropyl two bithiophene thiophene is coughed up) providing following structural formula to represent respectively and compd B (6-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) quinoxaline),
(2) by compd A (5,5 '-two iodo-1,1 '-dipropyl two bithiophene thiophene is coughed up) 5.0mmol, compd B (6-(4,4,5, 5-tetramethyl--1, 3,2-dioxaborolanes-2-base) quinoxaline) 15.0mmol, catalyzer (three (dibenzalacetone) two palladium) 0.15mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the K of glycol dimethyl ether 70mL, 2mol/L
2cO
3aqueous solution 35ml, Suzuki coupling reaction is carried out in mixed solution heating, 100 DEG C of back flow reaction 40h, the obtained organic semiconductor material 5 coughed up containing thiophene containing P2, 5 '-two (quinoxalin-6-yl)-1, the reaction solution that 1 '-dipropyl two bithiophene thiophene is coughed up, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the solid product 5 after purifying, 5 '-two (quinoxalin-6-yl)-1, 1 '-dipropyl two bithiophene thiophene is coughed up.The productive rate that this 5,5 '-two (quinoxalin-6-yl)-1,1 '-dipropyl two bithiophene thiophene is coughed up is 72%.
5,5 '-two (quinoxalin-6-yl)-1,1 '-dipropyl two bithiophene thiophene prepared by the present embodiment 2 is coughed up compound and carries out mass spectroscopy and ultimate analysis, analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z535 (M
+).
Ultimate analysis: C
30h
26n
4s
2si, C, 67.43; H, 4.92; N, 10.44.
Embodiment 3:
Organic electroluminescent semiconductor material 5,5 '-two (quinoxalin-6-yl)-1,1 '-dihexyl two bithiophene thiophene that a kind of thiophene is coughed up is coughed up (called after DQDTHSi), and its molecular structural formula is as shown in following I 3:
This organic electroluminescent semiconductor material I
3preparation method comprise the steps:
(1) compd A (5,5 '-two iodo-1,1 '-dihexyl two bithiophene thiophene is coughed up) providing following structural formula to represent respectively and compd B (6-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) quinoxaline),
(2) by compd A (5,5 '-two iodo-1,1 '-dihexyl two bithiophene thiophene is coughed up) 5.0mmol, compd B (6-(4,4,5, 5-tetramethyl--1, 3,2-dioxaborolanes-2-base) quinoxaline) 12.5mmol, catalyzer (two (triphenylphosphine) palladium chloride) 0.5mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the Cs of toluene solution 60mL, 2mol/L
2cO
3aqueous solution 40ml, Suzuki coupling reaction is carried out in mixed solution heating, 120 DEG C of back flow reaction 24h, the obtained organic semiconductor material 5 coughed up containing thiophene containing P3, 5 '-two (quinoxalin-6-yl)-1, the reaction solution that 1 '-dihexyl two bithiophene thiophene is coughed up, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the solid product 5 after purifying, 5 '-two (quinoxalin-6-yl)-1, 1 '-dihexyl two bithiophene thiophene is coughed up.The productive rate that this 5,5 '-two (quinoxalin-6-yl)-1,1 '-dihexyl two bithiophene thiophene is coughed up is 75%.
5,5 '-two (quinoxalin-6-yl)-1,1 '-dihexyl two bithiophene thiophene prepared by the present embodiment 3 is coughed up compound and carries out mass spectroscopy and ultimate analysis, analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z619 (M
+).
Ultimate analysis: C
36h
38n
4s
2si, C, 69.90; H, 6.15; N, 9.01.
Embodiment 4:
Organic electroluminescent semiconductor material 5,5 '-two (quinoxalin-6-yl)-1,1 '-phenylbenzene two bithiophene thiophene that a kind of thiophene is coughed up is coughed up (called after DQDTPSi), and its molecular structural formula is as shown in following I 4:
This organic electroluminescent semiconductor material I
4preparation method comprise the steps:
(1) compd A (5,5 '-two iodo-1,1 '-phenylbenzene two bithiophene thiophene is coughed up) providing following structural formula to represent respectively and compd B (6-(4,4,5,5-tetramethyl--1,3,2-dioxaborolanes-2-base) quinoxaline),
(2) by compd A (5,5 '-two iodo-1,1 '-phenylbenzene two bithiophene thiophene is coughed up) 5.0mmol, compd B (6-(4,4,5, 5-tetramethyl--1, 3,2-dioxaborolanes-2-base) quinoxaline) 10.5mmol, catalyzer (two (triphenylphosphine) palladium chloride) 0.5mmol joins in reaction flask, vacuumize, after logical nitrogen circulation 3 times, make reaction system be in anaerobic state, under nitrogen protection, add the Cs of toluene solution 60mL, 2mol/L
2cO
3aqueous solution 40ml, Suzuki coupling reaction is carried out in mixed solution heating, 115 DEG C of back flow reaction 24h, the obtained organic semiconductor material 5 coughed up containing thiophene containing P4, 5 '-two (quinoxalin-6-yl)-1, the reaction solution that 1 '-phenylbenzene two bithiophene thiophene is coughed up, described reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase sodium chloride aqueous solution is washed, dry, revolve to steam and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain the solid product 5 after purifying, 5 '-two (quinoxalin-6-yl)-1, 1 '-phenylbenzene two bithiophene thiophene is coughed up.The productive rate that this 5,5 '-two (quinoxalin-6-yl)-1,1 '-phenylbenzene two bithiophene thiophene is coughed up is 53%.
5,5 '-two (quinoxalin-6-yl)-1,1 '-phenylbenzene two bithiophene thiophene prepared by the present embodiment 4 is coughed up compound and carries out mass spectroscopy and ultimate analysis, analytical results is as follows:
Mass spectrometric measurement result is: MS:m/z603 (M
+).
Ultimate analysis: C
36h
22n
4s
2si, C, 71.67; H, 3.64; N, 9.33.
Performance test
DQDTMSi, DQDTPSi, DQDTHSi, DQDTPSi compound prepared by above-described embodiment 1-4 carries out thermal stability determination performance test, records result as follows respectively:
Thermal stability determination method: adopt thermogravimetric analyzer (TGA) to detect, analysis condition is nitrogen atmosphere, and when sweep velocity is 10 DEG C/min, analytical results is as shown in table 1:
The heat decomposition temperature of the organic semiconductor material in table 1 embodiment 1-4 and comparative example
As shown in Table 1, embodiment of the present invention organic electroluminescent semiconductor material has high heat decomposition temperature, its heat decomposition temperature is up to 400 DEG C more than (5% thermal weight loss), wherein, the heat decomposition temperature of the organic electroluminescent semiconductor material as embodiment 1 preparation that heat decomposition temperature is minimum is up to 401 DEG C, and the heat decomposition temperature of organic electroluminescent semiconductor material prepared by embodiment 4 is up to 420 DEG C.
In addition, through adopting time of flight method (Time of Flight, TOF) to detect, organic electroluminescent semiconductor material prepared by above-described embodiment 1 ~ 4 also has excellent carrier transmission performance.
Application Example 1:
Utilize prepared by above-described embodiment 45,5 '-two (quinoxalin-6-yl)-1,1 '-phenylbenzene two bithiophene thiophene is coughed up (called after DQDTPSi) and is prepared OLED, this OLED structure is with reference to Fig. 1, and it comprises glass substrate/ito anode layer (150nm)/NPB hole transmission layer (40nm)/DQDTPSi luminescent layer (the 20nm)/Alq stacking gradually combination
3electron transfer layer (40nm)/LiF buffer layer (1nm)/Al cathode layer (120nm).
Wherein, anode layer ITO(tin indium oxide) square resistance be the ITO of 10-20 Ω/mouth, each layer of OLED adopts the method preparation of vacuum evaporation, and the technique of vacuum evaporation is according to existing processing parameter setting.
OLED prepared by above-mentioned this application embodiment is carried out spectrum, light efficiency analysis.Wherein spectroscopic analysis as shown in Figure 3.As shown in Figure 3, should in the electroluminescent device of the use-case luminescent spectrum when voltage is 4.5V, its maximum emission wavelength is at 434nm.
At room temperature, test light efficiency under atmospheric environment, after measured, this Nan dian Yao achieves the maximum light efficiency of 5.5lm/W to OLED this application embodiment prepared.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. an organic electroluminescent semiconductor material, its general formula of molecular structure is following (I):
In formula, R is phenyl or C
1~ C
6alkyl.
2. organic electroluminescent semiconductor material according to claim 1, is characterized in that: described C
1~ C
6alkyl be C
3~ C
6alkyl.
3. prepare a method for organic electroluminescent semiconductor material as claimed in claim 1 or 2, comprise the steps:
Compd A, the B of following structural formula general formula are provided:
In anaerobic, alkaline environment and organo-metallic catalyst, under organic solvent existent condition, described compd A and B are carried out Suzuki linked reaction, and obtaining following general structure is the organic electroluminescent semiconductor material that (I) represents:
Wherein, the R in compd A, general structure (I) is phenyl or C
1~ C
6alkyl.
4. the method for organic electroluminescent semiconductor material according to claim 3, is characterized in that: the temperature of described Suzuki linked reaction is 75 ~ 120 DEG C, and the reaction times is 24 ~ 48 hours.
5. the method for organic electroluminescent semiconductor material according to claim 3, is characterized in that: the mol ratio of described compd A and B is 1:(2 ~ 3).
6. the method for organic electroluminescent semiconductor material according to claim 3, is characterized in that: the consumption of described organo-metallic catalyst and the mol ratio of compd A consumption are (0.05 ~ 0.1): 1.
7. according to the method for the arbitrary described organic electroluminescent semiconductor material of claim 3 ~ 6, it is characterized in that: described organo-metallic catalyst is organic palladium.
8. the method for organic electroluminescent semiconductor material according to claim 7, is characterized in that: described organic palladium is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, three (dibenzalacetone) two at least one in palladium.
9. the organic electroluminescent semiconductor material according to any one of claim 1 to 2 at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and application in organic laser apparatus.
10. the application of organic electroluminescent semiconductor material according to claim 9, it is characterized in that: described organic electroluminescence device comprises the anode layer, organic function layer, the cathode layer that stack gradually combination, wherein, the luminescent layer that described organic function layer is luminous under being included in the driving of additional power source, and described emitting layer material is the organic electroluminescent semiconductor material as described in any one of claim 1 to 2.
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| CN108047212A (en) * | 2018-01-08 | 2018-05-18 | 深圳市佶达德科技有限公司 | A kind of preparation method of double pyrazole acetic acid coumarin derivative laser material |
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| CN108047212A (en) * | 2018-01-08 | 2018-05-18 | 深圳市佶达德科技有限公司 | A kind of preparation method of double pyrazole acetic acid coumarin derivative laser material |
| CN108047212B (en) * | 2018-01-08 | 2023-03-10 | 深圳市佶达德科技有限公司 | Preparation method of bispyrazole acetic coumarin derivative laser material |
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