CN102557857B - Organic semiconductor material, and preparation method and application of organic semiconductor material - Google Patents
Organic semiconductor material, and preparation method and application of organic semiconductor material Download PDFInfo
- Publication number
- CN102557857B CN102557857B CN201010603038.XA CN201010603038A CN102557857B CN 102557857 B CN102557857 B CN 102557857B CN 201010603038 A CN201010603038 A CN 201010603038A CN 102557857 B CN102557857 B CN 102557857B
- Authority
- CN
- China
- Prior art keywords
- preparation
- semiconductor material
- organic
- organic semiconductor
- selenophen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 C*c1ccc2-c3c(C(*)(*)c4c-5cccc4)c-5c(C(*)(*)c4ccccc4-4)c-4c3C(*)(*)c2c1 Chemical compound C*c1ccc2-c3c(C(*)(*)c4c-5cccc4)c-5c(C(*)(*)c4ccccc4-4)c-4c3C(*)(*)c2c1 0.000 description 3
- YRBWPEYVEDKCEX-UHFFFAOYSA-N CC12c3c(Cc4c-5cccc4)c-5c(Cc4ccccc4-4)c-4c3CC1C=CC=C2 Chemical compound CC12c3c(Cc4c-5cccc4)c-5c(Cc4ccccc4-4)c-4c3CC1C=CC=C2 YRBWPEYVEDKCEX-UHFFFAOYSA-N 0.000 description 1
- SNWQUNCRDLUDEX-UHFFFAOYSA-N O=C1c2ccccc2C=C1 Chemical compound O=C1c2ccccc2C=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 description 1
- BCLXVBSQUQROKH-UHFFFAOYSA-N OB(c1ccc(-c2c(cccc3)c3cc3c2cccc3)[s]1)O Chemical compound OB(c1ccc(-c2c(cccc3)c3cc3c2cccc3)[s]1)O BCLXVBSQUQROKH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of light emitting materials and discloses an organic semiconductor material, and preparation method and application of the organic semiconductor material. The organic semiconductor material has the following general formula in the description, wherein R is C1-C12 alkyl; R1, R2 and R3 are selected from hydrogen atoms and a group shown in the description, and at most two of the R1, R2 and R3 are hydrogen atoms at the same time. The organic semiconductor material containing anthracene, selenophen and tripolyindene units has excellent thermal stability, good dissolubility and excellent hole and electron transmission performance; in addition, the introduction of electron withdrawing groups is favorable for blue shift of luminescent spectrum and for improving the electron transmission performance at the same time.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of organic semiconductor material containing anthracene, selenophen, three polyindenes.This aspect also relates to a kind of preparation method and application of organic semiconductor material.
Background technology
Along with the development of information age, there is the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating and be more and more subject to people's concern.OLED technology is paid close attention to by global scientist, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of novel LED technology, there is active illuminating, light, thin, good contrast, energy consumption organic electroluminescence device low, that can be made into the features such as flexible device material has been proposed to higher requirement.
1987, the Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research.And to realize the application purposes such as panchromatic demonstration and illumination, in three primary colours, blue light is absolutely necessary.Meanwhile, because blue light energy is the highest, as long as there is good material just can obtain green glow and ruddiness by several different methods.Therefore the luminescent properties that improves blue light is significant to realizing the panchromatic demonstration of organic electroluminescent and solid luminescence lighting tool.But because the energy of blue light is high, can gap length, efficiency and stability do not have green glow and red light material good, the carrier transmission performance of material neither be fine simultaneously.
Anthracene single crystal is the blue organic electroluminescent material using the earliest, but because its easy crystallization makes device unstable.In order to prevent its recrystallize, improve thermostability, C.W.Tang etc., at 9,10 substituting groups that introducing is large of anthracene, have synthesized ADN, and the device stability taking ADN as blue emitting material is greatly improved.
Selenophen, as one of the simplest 5-membered aromatic heterocycle, has important application at aspects such as organic synthesis, electro-conductive material and nonlinear optical materials.Selenophen character is similar to thiophene, can carry out the reactions such as halogenation, nitrated, sulfonation, acylations.Compared with S, the atomic radius of Se is large, and electronegativity is little simultaneously, and selenium atom more easily polarizes than sulphur atom, impels its initial oxidation current potential to reduce, and is conducive to the hole transport of material.And because selenium atom replaces sulphur atom, poly-selenophen has than the better thermostability of Polythiophene, and therefore the introducing of selenophen unit can also improve the thermostability of material.
Three polyindenes are highly symmetrical condensed-nuclei aromaticss, have been proved to be one of idealized compound of preparing liquid crystal material, fullerene derivate and C3 type asymmetry catalysis material etc.If three polyindenes can be carried out to suitable chemically modified, and construct novel organic conjugate functional materials as structural motif, will produce unique optics and photoelectronics behavior.
Summary of the invention
In order to address the above problem, the invention provides a kind of organic semiconductor material containing anthracene, selenophen, three polyindenes, there is following chemical general formula:
In formula, R is C
1-C
12alkyl; Preferably C
1-C
12straight chain or branched alkyl; R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously.
The present invention also provides the preparation method of above-mentioned organic semiconductor material, and step is as follows:
Step S1, provides following compd A and B;
Compd A is
or
or
in formula, R is C
1-C
12alkyl, preferably R is C
1-C
12straight chain or branched alkyl; B,
or
Step S2, in atmosphere of inert gases, is dissolved in compd A and B for 1: 1～1: 4.5 in the organic solvent that contains catalyzer with mol ratio, carries out Suzuki reaction 20～40h at 60～130 DEG C, makes general formula and is
described organic semiconductor material; In formula, R is C
1-C
12alkyl; R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously.
Wherein, in above-mentioned preparation method's step S2, described catalyzer is that organic palladium is (as Pd (PPh
3)
2cl
2, Pd
2(dba)
3), or be that organic palladium and organophosphor ligand are (as, P (o-Tol)
3) mixture (as Pd
2(dba)
3/ P (o-Tol)
3, and Pd
2(dba)
3: P (o-Tol)
3mol ratio be 1: 2～1: 4) mole dosage of described catalyzer is 0.005～0.10 times of compd A mole dosage; Described organic solvent is at least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or toluene.
The organic semiconductor material that the present invention makes can be applied to organic electroluminescent device, organic solar batteries, and organic field effect tube, organic optical memory, in organic non-linear optical properties or organic laser field.
Compared with prior art, a class prepared by the present invention is containing the organic semiconductor material of anthracene, selenophen, three polyindene unit, there is excellent thermostability, and such material has good solubility, the emission wavelength of this compounds is 460nm (± 20nm) left and right, belongs to blue light range; This class luminescent material is owing to containing the electron-withdrawing groups such as electron rich selenophen group and cyano group, aldehyde radical, nitro in structure, therefore material has had the performance of hole and electric transmission concurrently, is conducive to carrier transport, compound at luminescent layer, obtains high luminous efficiency; Separately, the introducing of electron-withdrawing group is conducive to make luminescent spectrum blue shift, and the introducing of electron-withdrawing group simultaneously is also conducive to improve the transmission performance of electronics.
Brief description of the drawings
Fig. 1 is the luminescent spectrum figure of the electroluminescent device that makes taking the AS3OT organic semiconductor material in embodiment 3 as luminescent layer in embodiment 4;
Fig. 2 is the structural representation of the electroluminescent device that makes taking the AS3OT organic semiconductor material in embodiment 3 as luminescent layer in embodiment 4.
Embodiment
The invention provides a kind of organic semiconductor material containing anthracene, selenophen, three polyindenes, there is following chemical general formula:
In formula, R is C
1-C
12alkyl; Preferably C
1-C
12straight chain or branched alkyl; R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously.
The present invention also provides the preparation method of above-mentioned organic semiconductor material, and step is as follows:
Step S1, provides following compd A, i.e. bromo or iodo-alkyl three polyindenes, and compd B, i.e. 5-(anthracene-9-yl) selenophen-2-ylboronic acid or 5-(anthracene-9-yl) selenophen-2-ylboronic acid ester;
Compd A is
or
or
in formula, R is C
1-C
12alkyl, preferably R is C
1-C
12straight chain or branched alkyl;
Compd B is
or
Step S2, in atmosphere of inert gases (comprising nitrogen or argon gas etc.), is dissolved in compd A and B for 1: 1～1: 4.5 in the organic solvent that contains catalyzer with mol ratio, carries out Suzuki reaction 20～40h at 60～130 DEG C, makes general formula and is
described organic semiconductor material; In formula, R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously; Reaction formula is as follows:
Wherein, in above-mentioned preparation method's step S2, described catalyzer is organic palladium, or is the mixture (mol ratio of organic palladium and organophosphor ligand 1: 2～1: 4) of organic palladium and organophosphor ligand; The mole dosage of described catalyzer is 0.005～0.10 times of compd A material mole dosage; Described organic solvent is at least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or toluene.
The organic semiconductor material that the present invention makes can be applied to organic electroluminescent device, organic solar batteries, and organic field effect tube, organic optical memory, in organic non-linear optical properties or organic laser field.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The present embodiment openly organic compound containing anthracene, selenophen, three polyindene unit of following structure (is organic semiconductor material, lower same) 2-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes (AS1ET):
The preparation of step 1, three polyindenes:
1-indone 10mmol is joined in the mixing solutions containing acetic acid (HOAc) 8mL and concentrated hydrochloric acid 4mL, be heated to 100 DEG C, stirring and refluxing 20h.After reaction finishes, reaction solution is poured in the beaker that frozen water is housed, had immediately a large amount of solid precipitations to produce.Precipitate successively after water, acetone and washed with dichloromethane, obtain white solid powder three polyindenes, productive rate: 91%.EI-MS：m/z?342(M
+)。
Step 2,5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes:
Three polyindene 8mmol are added in reaction flask; vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state; under nitrogen protection, inject anhydrous tetrahydro furan 50mL, system is cooled to-78 DEG C by dry ice/acetone batch, be slowly added dropwise to the hexane solution of n-Butyl Lithium 56mmol; three polyindene solids dissolve completely; after about 0.5h, system is got back to room temperature naturally, then reacts 0.5h.Again be cooled to after-78 DEG C, drip 1-bromic ether 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add large water gaging react with quencher and use dichloromethane extraction, revolve and steam except desolventizing, obtain crude product, through silica gel column chromatography separating-purifying, eluent is sherwood oil, finally obtain light yellow crystal 5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 72%.EI-MS：m/z510(M
+)。
Step 3,2-be iodo-5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes:
By 5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindene 5mmol join 15ml by CH
3cOOH, H
2sO
4, H
2o, CCl
4in the solution that these four kinds of compound form, (wherein the ratio of four kinds of compounds is CH
3cOOH: H
2sO
4: H
2o: CCl
4=100: 5: 20: 8), be heated to 40 DEG C.Add HIO
31.67mmol and I
21.67mmol, in front mixed reaction system, is heated to 80 DEG C, and stirring reaction 4.5h.After reaction finishes, mixed solution cool to room temperature, suction filtration, washing.What obtain is deposited in the 2h that refluxes in methyl alcohol, cool to room temperature, suction filtration, finally obtain white powder 2-iodo-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 67%.MALDI/TOF-MS：m/z：637(M
+)。
The preparation of step 4, (5-(anthracene-9-yl) selenophen)-2-ylboronic acid:
The preparation of 9-(selenophen-2-yl) anthracene
9-bromine anthracene 10mmol is joined in reaction flask; vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state, under nitrogen protection, add and be dissolved with the anhydrous tetrahydrofuran solution 50mL of 2-selenophen boric acid 5.5mmol, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2cO
3aqueous solution 34ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, eluent is V (sherwood oil): V (methylene dichloride)=10: 1, finally obtains white solid 9-(selenophen-2-yl) anthracene.Productive rate: 96%.EI-MS：m/z308(M
+)。
The preparation of 9-(5-bromine selenophen-2-yl)-anthracene
9-(selenophen-2-yl) anthracene 8mmol is dissolved in 25mL methylene dichloride, simultaneously by bromizating agent, as, N-bromo-succinimide (NBS, lower same) 8mmol is dissolved in 10mL methylene dichloride (CH
2cl
2) in, under 0 DEG C of condition, the dichloromethane solution of NBS is slowly splashed in the reaction flask that contains 9-(selenophen-2-yl) anthracene, splash into 1ml Glacial acetic acid, lucifuge reaction 12h.After reaction finishes, mixed solution washs with dilute hydrochloric acid, extracts to obtain bottom organic liquor, dry, revolves to steam except after desolventizing to obtain crude product, and recrystallization in the mixed solvent of normal hexane/methylene dichloride, obtains yellow solid 9-(5-bromine selenophen-2-yl)-anthracene.Productive rate: 92%.EI-MS：m/z386(M
+)。
The preparation of 5-(anthracene-9-yl) selenophen-2-ylboronic acid
9-(5-bromine selenophen-2-yl)-anthracene 7mmol is joined in reaction flask; vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state; under nitrogen protection, inject anhydrous tetrahydro furan (THF) (50mL); system is cooled to-78 DEG C by dry ice/acetone batch, is slowly added dropwise to the normal hexane ((CH of n-Butyl Lithium (n-BuLi) 10.5mmol
3o)
3b) solution, solid dissolves completely, at same temperature, stirs this mixture 1h, in reaction mixture, drips rapidly trimethyl borate, and temperature of reaction is slowly increased to room temperature, stirs this reaction mixture 12h.In the time that reaction completes, add therein 1M hydrochloric acid soln 500ml, stir the mixture 3.5h forming.With frozen water cancellation reaction, sodium-chlor washing, ethyl acetate extraction, dry, revolve steaming and obtain crude product except after desolventizing.Recrystallization in the mixed solvent of normal hexane/methylene dichloride, obtains white solid, productive rate: 70%.EI-MS：m/z352(M
+)。
Step 5,2-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes (AS1ET):
By iodo-2-5; 5 '; 10; 10 '; 15,15 '-Hexaethyl, three polyindene 3mmol join in reaction flask, vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state, under nitrogen protection, add the anhydrous tetrahydrofuran solution 50mL, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L that are dissolved with 5-(anthracene-9-yl) selenophen-2-ylboronic acid 3.1mmol
2cO
3aqueous solution 34ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, eluent is that eluent is V (sherwood oil): V (methylene dichloride)=12: 1, finally obtains general formula and is
yellow solid 2-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 86%.MALDI/TOF-MS：m/z：816(M
+)。
Embodiment 2
The present embodiment is the organic compound 2 containing anthracene, selenophen, three polyindene unit of following structure openly, 7-bis-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes (AS2ET):
Wherein, 5,5 ', 10,10 ', the preparation of the preparation of 15,15 '-Hexaethyl, three polyindenes and (5-(anthracene-9-yl) selenophen)-2-ylboronic acid, in the same manner as in Example 1.
Step 1,2,7-bis-is bromo-5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes:
By 5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindene 5mmol are dissolved in 25mL methylene dichloride, by bromizating agent, as NBS 10.5mmol is dissolved in 10mL methylene dichloride, under 0 DEG C of condition, the dichloromethane solution of NBS is slowly splashed in the reaction flask that contains 9-(selenophen-2-yl) anthracene simultaneously, splash into 1ml Glacial acetic acid, lucifuge reaction 12h.After reaction finishes, mixed solution washs with dilute hydrochloric acid, extracts to obtain bottom organic liquor, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, recrystallization in the mixed solvent of normal hexane and methylene dichloride, obtaining yellow crystals 2,7-bis-is bromo-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 43%.MALDI/TOF-MS：m/z：666(M
+)。
Step 2,2,7-bis-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes (AS2ET): preparation:
By 2; 7-tri-bromo-5; 5 '; 10,10 ', 15; 15 '-Hexaethyl, three polyindene 4mmol join in reaction flask; vacuumize, after logical nitrogen circulation 3 times, make reaction system in anaerobic state, under nitrogen protection, add the anhydrous tetrahydrofuran solution 50mL, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L that are dissolved with 5-(anthracene-9-yl) selenophen-2-ylboronic acid 8.2mmol
2cO
3aqueous solution 34ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve to steam except after desolventizing and obtain crude product, through silica gel column chromatography separating-purifying, eluent is that eluent is V (sherwood oil): V (methylene dichloride)=10: 1, finally obtains yellow solid 2,7-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 82%.MALDI/TOF-MS：m/z?1122(M
+)。
Embodiment 3
The present embodiment is the organic compound containing anthracene, selenophen, three polyindene unit of following structure openly:
2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes (AS3ET);
2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindenes (AS3HT); And
2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-octyl three polyindenes (AS3OT):
One, 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes (AS3ET):
Wherein, 5,5 ', 10,10 ', the preparation of the preparation of 15,15 '-Hexaethyl, three polyindenes and (5-(anthracene-9-yl) selenophen)-2-ylboronic acid, in the same manner as in Example 1.
Step 1,2,7,12-tri-is bromo-5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes:
By 5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindene 5mmol are dissolved in 25mL methylene dichloride, bromine 1mL is dissolved in 10mL methylene dichloride simultaneously, under 0 DEG C of condition, the dichloromethane solution of bromine is slowly splashed into contain 5,5 ', 10,10 ', 15, in the reaction system of 15 '-Hexaethyl, three polyindenes, after bromine drips, system is got back to room temperature naturally, lucifuge reaction 12h.After reaction finishes, mixed solution is removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, dry, revolves to steam except after desolventizing to obtain crude product, recrystallization in ethanol, obtaining yellow crystals 2,7,12-tri-is bromo-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 91%.MALDI-TOF：m/z744(M
+)。
Step 2,2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes (AS3ET): preparation:
AS3ET
By 2; 7; 12-tri-is bromo-5,5 ', 10; 10 '; 15,15 '-Hexaethyl, three polyindene 3.5mmol join in reaction flask, vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state, under nitrogen protection, add the anhydrous tetrahydrofuran solution 50mL, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L that are dissolved with 5-(anthracene-9-yl) selenophen-2-ylboronic acid 11mmol
2cO
3aqueous solution 34ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve and steam except obtaining crude product after desolventizing, through silica gel column chromatography separating-purifying, eluent is that eluent is V (sherwood oil): V (methylene dichloride)=8: 1, finally obtain yellow solid 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-Hexaethyl, three polyindenes.Productive rate: 79%.MALDI/TOF-MS：m/z?1428(M
+)。
Two, 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyl three polyindenes (AS3HT):
Wherein, 5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes is in the same manner as in Example 1.
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyl three polyindenes:
Three polyindene 8mmol are added in reaction flask; vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state; under nitrogen protection, inject anhydrous tetrahydro furan 50mL, system is cooled to-78 DEG C by dry ice/acetone batch, be slowly added dropwise to the hexane solution of n-Butyl Lithium 56mmol; three polyindene solids dissolve completely; after about 0.5h, system is got back to room temperature naturally, then reacts 0.5h.Again be cooled to after-78 DEG C, drip 1-bromo normal hexane 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add large water gaging react with quencher and use dichloromethane extraction, revolve and steam except desolventizing, obtain crude product, through silica gel column chromatography separating-purifying, eluent is sherwood oil, finally obtain yellow solid 5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindenes.Productive rate: 74%.MALDI-TOF：m/z847(M
+)。
Step 2,2,7,12-tri-is bromo-5,5 ', 10,10 ', the preparation of 15,15 '-six n-hexyl three polyindenes:
By 5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindene 5mmol are dissolved in 25mL methylene dichloride, bromine 1mL is dissolved in 10mL methylene dichloride simultaneously, under 0 DEG C of condition, the dichloromethane solution of bromine is slowly splashed into contain 5,5 ', 10,10 ', 15, in the reaction system of 15 '-six n-hexyl three polyindenes, after bromine drips, system is got back to room temperature naturally, lucifuge reaction 12h.After reaction finishes, mixed solution is removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, dry, revolves to steam except after desolventizing to obtain crude product, recrystallization in ethanol, obtaining yellow crystals 2,7,12-tri-is bromo-5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindenes.Productive rate: 93%.MALDI-TOF：m/z1081(M
+)。
Step 3,2-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-5-(anthracene-9-yl) selenophen preparation:
Vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state; under nitrogen protection, in reaction flask, add 9-(5-bromine selenophen-2-yl)-anthracene 7mmol; inject anhydrous tetrahydro furan (80mL); system is cooled to-78 DEG C by dry ice/acetone batch; the hexane solution that is slowly added dropwise to n-Butyl Lithium 10.5mmol, solid dissolves completely, at same temperature, stirs this mixture 1.5h.Then under-78 DEG C of conditions, use and inject 2-isopropoxy-4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane 12mmol of 3,2-bis-, temperature of reaction is slowly increased to room temperature, stirs this reaction mixture 12h.After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, filters, and revolves to steam except after desolventizing to obtain crude product.Through silica gel column chromatography separating-purifying, eluent is V (sherwood oil): V (ethyl acetate)=12: 1, finally obtains pulverulent solids 2-(4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-5-(anthracene-9-yl) selenophen.Productive rate: 62%.EI-MS：m/z434(M
+)。
Step 4,2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindenes (AS3HT): preparation:
By bromo-2,7,12-tri-5; 5 ', 10,10 '; 15,15 '-six n-hexyl three polyindene 3mmol join in reaction flask, vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state, under nitrogen protection, add and be dissolved with 2-(4,4; 5; 5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-)-5-(anthracene-9-yl) the anhydrous tetrahydrofuran solution 60mL of selenophen 9.5mmol, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L
2cO
3aqueous solution 40ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve and steam except obtaining crude product after desolventizing, through silica gel column chromatography separating-purifying, eluent is that eluent is V (sherwood oil): V (methylene dichloride)=9: 1, finally obtain yellow solid 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-hexyl three polyindenes.Productive rate: 72%.MALDI/TOF-MS：m/z?1764(M
+)。
Three, 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyl three polyindenes (AS3OT):
Wherein, 5,5 ', 10,10 ', the preparation of 15,15 '-Hexaethyl, three polyindenes is in the same manner as in Example 1.
Step 1,5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyl three polyindenes:
Three polyindene 8mmol are added in reaction flask; vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state; under nitrogen protection, inject anhydrous tetrahydro furan 50mL, system is cooled to-78 DEG C by dry ice/acetone batch, be slowly added dropwise to the hexane solution of n-Butyl Lithium 56mmol; three polyindene solids dissolve completely; after about 0.5h, system is got back to room temperature naturally, then reacts 0.5h.Again be cooled to after-78 DEG C, drip 1-n-octane bromide 53.8mmol in this reaction system, and at room temperature react 3h.After question response just finishes, add large water gaging react with quencher and use dichloromethane extraction, revolve and steam except desolventizing, obtain crude product, through silica gel column chromatography separating-purifying, eluent is sherwood oil, finally obtain yellow solid 5,5 ', 10,10 ', 15,15 '-six n-octyl three polyindenes.Productive rate: 70%.MALDI-TOF：m/z1015(M
+)。
Step 2,2,7,12-tri-is bromo-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyl three polyindenes:
By 5,5 ', 10,10 ', 15,15 '-six n-octyl three polyindene 5mmol are dissolved in 25mL methylene dichloride, bromine 1mL is dissolved in 10mL methylene dichloride simultaneously, under 0 DEG C of condition, the dichloromethane solution of bromine is slowly splashed into contain 5,5 ', 10,10 ', 15, in the reaction system of 15 '-six n-octyl three polyindenes, after bromine drips, system is got back to room temperature naturally, lucifuge reaction 12h.After reaction finishes, mixed solution is removed unnecessary bromine with saturated aqueous sodium thiosulfate and saturated common salt water washing, dry, revolves to steam except after desolventizing to obtain crude product, recrystallization in ethanol, obtaining yellow crystals 2,7,12-tri-is bromo-5,5 ', 10,10 ', 15,15 '-six n-octyl three polyindenes.Productive rate: 90%.MALDI-TOF：m/z1249(M
+)。
Step 3,2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', the preparation of 15,15 '-six n-octyl three polyindenes (AS30T):
By 2; 7; 12-tri-is bromo-5,5 ', 10; 10 '; 15,15 '-six n-octyl three polyindene 3.2mmol join in reaction flask, vacuumize, after logical nitrogen circulation 3 times; make reaction system in anaerobic state, under nitrogen protection, add the anhydrous tetrahydrofuran solution 50mL, the Na of tetra-triphenylphosphine palladium 0.01mmol, 2mol/L that are dissolved with 5-(anthracene-9-yl) selenophen-2-ylboronic acid 10mmol
2cO
3aqueous solution 34ml, is heated to 65-70 DEG C of back flow reaction 20h by mixed solution.After reaction finishes, reaction solution is poured in the aqueous solution of saturated ammonium chloride, ethyl acetate extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve and steam except obtaining crude product after desolventizing, through silica gel column chromatography separating-purifying, eluent is that eluent is V (sherwood oil): V (methylene dichloride)=10: 1, finally obtain yellow solid 2,7,12-tri-(5-(anthracene-9-yl) selenophen-2-yl)-5,5 ', 10,10 ', 15,15 '-six n-octyl three polyindenes.Productive rate: 77%.MALDI/TOF-MS：m/z1933(M
+)。
Embodiment 4
AS3OT in employing embodiment 3 does the making of the OLED device of luminescent layer:
The materials A S3OT obtaining by previous embodiment is as luminescent layer, with the method fabricate devices of vacuum evaporation.With ito glass (Glass), for anode, (wherein ITO is tin indium oxide, play electric action), NPB (N, N '-bis-(Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines) be hole transmission layer, AS3OT is luminescent layer, BCP (2,9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline) be hole blocking layer, Alq
3(oxine aluminium) is electron transfer layer, and LiF layer is buffer layer, and Al layer is negative electrode, prepares luminescent device, and the OLED device architecture obtaining is: glass/ITO/NPB/AS3OT/BCP/Alq
3/ LiF/Al, as shown in Figure 2.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. the organic semiconductor material of following general formula,
In formula, R is C
1-C
12alkyl; R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously.
2. a preparation method for organic semiconductor material, is characterized in that, comprises the steps:
Step S1, provides following compd A and B;
Compd A is
In formula, R is C
1-C
12alkyl;
Compd B is
Step S2, in atmosphere of inert gases, is dissolved in compd A and B in the organic solvent that contains catalyzer, carries out Suzuki reaction 20～40h at 60～130 DEG C, makes general formula and is
described organic semiconductor material; In formula, R
1, R
2, R
3be selected from hydrogen atom and
and R
1, R
2, R
3in maximum two be hydrogen atom simultaneously.
3. preparation method according to claim 2, is characterized in that, in described step S2, and mol ratio 1:1～1:4 of described compd A and B.
4. preparation method according to claim 2, is characterized in that, in described step S2, described catalyzer is organic palladium.
5. preparation method according to claim 2, is characterized in that, in described step S2, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. preparation method according to claim 5, is characterized in that, in the mixture of described organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1:2～1:4.
7. according to the preparation method described in claim 2,4 or 5, it is characterized in that, the mole dosage of described catalyzer is 0.005-0.10 times of compd A mole dosage.
8. preparation method according to claim 2, is characterized in that, in described step S2, described organic solvent is at least one in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene or toluene.
9. the application of organic semiconductor material claimed in claim 1 in organic electroluminescent device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010603038.XA CN102557857B (en) | 2010-12-23 | 2010-12-23 | Organic semiconductor material, and preparation method and application of organic semiconductor material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010603038.XA CN102557857B (en) | 2010-12-23 | 2010-12-23 | Organic semiconductor material, and preparation method and application of organic semiconductor material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102557857A CN102557857A (en) | 2012-07-11 |
| CN102557857B true CN102557857B (en) | 2014-07-23 |
Family
ID=46404640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010603038.XA Expired - Fee Related CN102557857B (en) | 2010-12-23 | 2010-12-23 | Organic semiconductor material, and preparation method and application of organic semiconductor material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102557857B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6355894B2 (en) * | 2013-04-16 | 2018-07-11 | 出光興産株式会社 | Anthracene derivative and organic electroluminescence device using the same |
| CN107778280B (en) * | 2017-02-24 | 2021-01-19 | 华南理工大学 | Star-shaped symmetrical organic solar cell micromolecule receptor material based on truxene, preparation method thereof and organic solar cell |
| CN109293886A (en) * | 2018-09-30 | 2019-02-01 | 河北科技大学 | The preparation method and application of microporous polymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4140882B2 (en) * | 2002-03-06 | 2008-08-27 | 靖彦 城田 | Torquesen derivatives |
| JP2008536811A (en) * | 2005-03-11 | 2008-09-11 | メルク パテント ゲーエムベーハー | Monomers, oligomers and polymers containing thiophene and selenophene |
| CN101139319B (en) * | 2007-10-17 | 2010-05-19 | 华东师范大学 | Substituted quinoline trimer indene derivative and method for making same |
| CN101333439A (en) * | 2008-06-27 | 2008-12-31 | 南京邮电大学 | Organic photoelectric functional material based on trisubstituted triindene structure unit and uses thereof |
-
2010
- 2010-12-23 CN CN201010603038.XA patent/CN102557857B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102557857A (en) | 2012-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384613B (en) | A kind of new electroluminescent organic material and its preparation method and application | |
| CN102653546B (en) | Bipolarity Blue-light emitting host material and preparation method thereof and organic electroluminescence device | |
| CN108658940A (en) | Thermal activation delayed fluorescence material, its synthetic method and OLED luminescent devices | |
| CN102464650B (en) | Organic semiconductor material containing anthracene, thiofuran and truxene and preparation method and application of organic semiconductor material | |
| CN111689962A (en) | Compound with benzimidazole pyridine as receptor and application thereof | |
| CN103073534B (en) | Organic semiconductor material, and preparation method and application thereof | |
| CN106187963A (en) | One is containing anthracene compounds and preparation method thereof and a kind of organic luminescent device | |
| CN109232376A (en) | A kind of fluorene derivative and its organic electroluminescence device | |
| CN110964019B (en) | Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof | |
| CN102557857B (en) | Organic semiconductor material, and preparation method and application of organic semiconductor material | |
| CN113416175B (en) | Compound with anthracene benzofuran as core framework and application thereof | |
| CN111574505B (en) | Compound with benzo [ c ] cinnoline as receptor and application thereof | |
| CN102653677B (en) | Bipolar blue-light main material and preparation method thereof and organic electroluminescent device | |
| CN103288811B (en) | Containing dibenzothiophene sulphone organic semiconductor material, its preparation method and organic electroluminescence device | |
| CN102807554B (en) | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof | |
| CN102838585B (en) | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof | |
| CN102850320B (en) | Compound containing dibenzothiophene sulfone and preparation method and application thereof | |
| CN102558168B (en) | Organic semiconductor material and preparation method and application thereof | |
| CN102676155B (en) | Material containing anthracene, diazosulfide and trimer indene and preparing method and application therefore | |
| CN102807534B (en) | Organic semiconductor material and preparation method thereof | |
| CN102719236B (en) | Bipolar blue light-emitting host material and preparation method thereof, and organic electroluminescent device using bipolar blue light-emitting host material | |
| CN102807556B (en) | Organic semiconductor material containing naphthalene, anthracene, dibenzothiophene sulfone units and preparation method and application thereof | |
| CN102464978B (en) | Conductive cavity-type blue electroluminescent material and preparation method and application thereof | |
| CN106588592A (en) | Dianthranide derivative, preparation method, and application thereof | |
| CN102807535B (en) | Organic semiconductor material, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140723 Termination date: 20181223 |