CN103848968A - Polymer containing thienopyrrole dione-dibenzothiophene benzodithiophene, preparation method and application thereof - Google Patents

Polymer containing thienopyrrole dione-dibenzothiophene benzodithiophene, preparation method and application thereof Download PDF

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CN103848968A
CN103848968A CN201210495110.0A CN201210495110A CN103848968A CN 103848968 A CN103848968 A CN 103848968A CN 201210495110 A CN201210495110 A CN 201210495110A CN 103848968 A CN103848968 A CN 103848968A
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thiophene
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CN103848968B (en
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周明杰
管榕
李满园
黄佳乐
黎乃元
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The present invention provides a polymer containing thienopyrrole dione-dibenzothiophene benzodithiophene, a preparation method and an application thereof. The polymer is a polymer P having the following general formula, wherein R1 and R2 are H and C1-C10 alkyl, C1-C10 alkoxy or alkylthiophene group, R3 is C1-C14 alkyl, R4 and R5 are H or C2-C12 alkyl, the simple structure formula of the alkylthiophene group is as the follow, R' is C6-C10 alkyl, and n is a natural number of 1-80. According to the present invention, the polymer contains the new dibenzothiophene benzodithiophene and thienopyrrole-4,6-dione unit, has the new conjugate plane structure, has characteristics of excellent sunlight matching property, excellent carrier mobility property and simple and controllable preparation method, and has good application prospects in the fields of polymer solar cells, organic electroluminescent devices and other optoelectronic materials. The polymer P is as the follow.

Description

A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers and preparation and application thereof
Technical field
The present invention relates to photoelectric material technical field, particularly relate to a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophene-based conjugated polymerss and preparation method thereof and application.
Background technology
Organic solar batteries is owing to having some incomparable advantages of inorganic solar cell, as with low cost, manufacture craft is simple, and product weight is light, the advantage such as can large area flexible prepares and gets more and more people's extensive concerning as the potential renewable energy source of one.In the past ten years, the performance of organic solar batteries is steadily improved, and effciency of energy transfer has approached 10%.But up to the present, the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.
The effciency of energy transfer of organic polymer solar cell is still low than silicon solar cell at present, one of reason be polymkeric substance carrier mobility than the mobility of inorganic monocrystal material low several orders of magnitude, and the absorption spectrum of polymkeric substance photocell material can not mate well with solar spectrum, it is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor, improve the efficiency that absorbs to sunlight.
One of method that improves the effciency of energy transfer of polymer solar battery is synthesizing new P-type conjugated polymers, and novel P-type conjugated polymers need to possess following characteristics: (a) good solubility, be beneficial to solvent processing, and realize suitability for industrialized production; (b) whole solar spectrum is had to wide and strong absorption; (c) carrier mobility is high, is beneficial to carrier transport.Wherein, how to widen the light abstraction width of polymkeric substance by the emphasis that is research, by selecting suitable structural unit composition semi-conducting polymer, be beneficial to the light abstraction width of polymkeric substance is widened to infrared, near-infrared region.For realizing the commercialization of organic solar batteries, develop new polymer materials, improve the effciency of energy transfer of photoelectric material for the great significance of organic solar batteries.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers.
The present invention also aims to provide preparation method and the application containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers.
First aspect, the invention provides a kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, for having the polymer P of following general formula:
P:
Figure BDA00002482100300021
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is:
Figure BDA00002482100300022
r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
Contain dibenzo [b of the present invention containing in the structure of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene units, this unit is to obtain by the benzene 1,4-Dithiapentalene with plane rigid structure is derivative, benzo two thiophene units have higher carrier mobility speed and thermostability, are used widely in field of photovoltaic materials.And dibenzothiophene benzene 1,4-Dithiapentalene has expanded conjugated backbone on the conjugated structure basis of original benzene 1,4-Dithiapentalene, there is unique keystone ring heptacene rigid planar structure, can effectively reduce the bandwidth of polymkeric substance, the transfer of current carrier in molecular skeleton become to be more prone to, improve carrier mobility speed, make polymkeric substance there is good thermostability and environmental stability simultaneously.In addition, by introduce the heteroatoms such as nitrogen, sulphur in the trapezoidal conjugated structure of this heptacene unit, the band gap of adjustable polymkeric substance and photo absorption performance, make the polymkeric substance that contains dibenzothiophene benzo two thiophene units have good application prospect in organic photoelectrical material field.
Meanwhile, contain thieno-[3,4-c] pyrroles-4 of the present invention containing in Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer structures, 6-dione unit, this unit is the body unit that is subject to of excellent property, first, the two dimensional structure that it has, is beneficial to electronics along polymer backbone delocalization; Secondly, thieno-[3,4-c] pyrroles-4, the strong sucting electronic effect that 6-dione unit has can regulate HOMO and the lumo energy of subject polymer effectively, meanwhile, introduces alkyl and can effectively improve its solvability on N atom.Therefore, the application of this structural unit in the photoelectric materials such as Organic Light Emitting Diode, organic solar batteries, field-effect transistor is very extensive.
Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers that contain of the present invention contain above two kinds of unit, have new conjugate planes structure, and excellent sunlight matching and carrier mobility performance, and effciency of energy transfer is high, has a extensive future.
Second aspect, the invention provides a kind of preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, comprises following operation steps:
Compd A and compd B are provided, and the structural formula of compd A and B is respectively:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is:
Figure BDA00002482100300032
r ' is C 6~ C 10alkyl;
Under protection of inert gas; 1:1 ~ 1:1.5 adds compd A and compd B in organic solvent in molar ratio; add catalyzer; carry out Stille coupling reaction 24 ~ 72 hours at 60 ~ 120 ℃; after separation and purification, obtain containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, described is the polymer P with following general formula containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers:
P:
Figure BDA00002482100300041
In formula, n is the natural number between 1 ~ 80.
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compd A mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compd A mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
Preferably, described rare gas element is nitrogen.
Preferably, described organic solvent is the one in toluene, tetrahydrofuran (THF) (THF) and DMF (DMF), and solvent is enough.Solvent for use is dried before use, and reaction is carried out under water-less environment.
Preferably, the operation of described separation and purification is specially: remove reaction solution under reduced pressure organic solvent, surplus materials is added drop-wise to and in methyl alcohol, carries out sedimentation, suction filtration, with dry after methanol wash, then carries out separating-purifying take chloroform as elutriant with alumina chromatographic column, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, and obtains containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers.
The reaction formula of described Stille coupling reaction is:
Figure BDA00002482100300051
Preferably; the operating process of described Stille coupling reaction is: under protection of inert gas; compd A is added in organic solvent and mixed with compd B; logical rare gas element bubbling 0.5h removes residual oxygen; add rapidly catalyzer; logical rare gas element bubbling 1h removes after residual oxygen again, is warming up to 60 ~ 120 ℃ of stirring and refluxing reaction 24 ~ 72h, obtains containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers after separation and purification.
The preparation method of described compd A comprises following operation steps:
(1) under protection of inert gas; compound a is added in tetrahydrofuran (THF) (THF); be cooled to-78 ℃; slowly add n-Butyl Lithium (n-BuLi); compound a: the mol ratio of n-Butyl Lithium (n-BuLi) is 1:2.2 ~ 1:2.5; then stirring reaction 2h at-78 ℃, then add trimethyltin chloride (Me 3snCl), compound a: trimethyltin chloride (Me 3snCl) mol ratio is 1:2 ~ 1:2.5, returns to room temperature after insulation reaction 0.5h, continues reaction 24h, obtains compound b, and reaction formula is:
Preferably, described n-Butyl Lithium (n-BuLi) is 2.5:1 with the mol ratio of compound a, trimethyltin chloride (Me 3snCl) be 2.5:1 with the mol ratio of compound a.
(2) under rare gas element and oxygen free condition, the compound b that is 1:2 ~ 1:2.5 by mol ratio and compound c 2-brooethyl thionyl benzene add in solvent, add catalyzer, at 80 ℃, Stille coupling reaction 48h occur, and obtain compound d, and reaction formula is:
Figure BDA00002482100300061
Preferably, described solvent is DMF (DMF), toluene or tetrahydrofuran (THF) (THF).
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compound b mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compound b mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
(3) in trifluoromethanesulfonic acid, after compound d reacts with Vanadium Pentoxide in FLAKES, pour reactant in ice-water bath cancellation reaction, be precipitated, gained precipitation is added in pyridine and carries out back flow reaction, obtain Verbindung, reaction formula is:
Figure BDA00002482100300062
Preferably, described reaction with Vanadium Pentoxide in FLAKES is at room temperature reaction 72h, and the mol ratio of described compound d and Vanadium Pentoxide in FLAKES is 1.5:1 ~ 2.0:1, and the temperature of described back flow reaction is 110 ℃, and the reaction times is 12h.
(4) under lucifuge condition, there is bromination reaction with Verbindung in N-bromo-succinimide (NBS), obtain compd A in dimethyl formamide (DMF), and reaction formula is:
Figure BDA00002482100300071
Preferably, described N-bromo-succinimide (NBS): the mol ratio of Verbindung is 3:1, described bromination reaction is at room temperature to react 15h.
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, the skeleton symbol of described alkylthrophene group is:
Figure BDA00002482100300072
r ' is C 6~ C 10alkyl.
In embodiment below, for convenience of statement, the compd A of different substituents is used respectively A1, A2, A3, A4, A5, A6, A7 etc. represent, intermediate reaction thing and product also according to said method represent, the compound a a1 of for example different substituents, a2, a3 etc. represent, name and are as the criterion with the title in each embodiment.
The preparation method of described compd B comprises following operation steps:
I, compound f thiophene-3, there is condensation reaction in 4-dioctyl phthalate, obtain the crude product of compound g in acetic anhydride, and described crude product reacts with thionyl chloride after reacting with compound h again, obtains compound i, and reaction formula is:
Figure BDA00002482100300073
Preferably, described setting-up point is 140 ℃, and the time is 12h; The mol ratio of described compound ￡ compound h is 1:1.2 ~ 1:1.5; Described and compound h temperature of reaction is 110 ℃, and the reaction times is 24h, and described temperature of reacting with thionyl chloride is 80 ℃, and the time is 4h.
Under II, lucifuge condition, in the mixed solution of sulfuric acid and trifluoroacetic acid formation, compound i at room temperature reacts and spends the night with N-bromo-succinimide (NBS), obtains compound j, and reaction formula is as follows:
Figure BDA00002482100300081
Preferably, described sulfuric acid is that massfraction is 98% the vitriol oil, and the mol ratio of described compound i:N-bromo-succinimide (NBS) is 1:3, and described N-bromo-succinimide (NBS) point adds for four times.
III, in anaerobic and atmosphere of inert gases, compound j and compound k are added in tetrahydrofuran (THF) with mol ratio 1:2, add catalyzer, be heated to 60 ℃ and carry out Stille coupling reaction 24h, obtain compound n, reaction formula is:
Figure BDA00002482100300082
Preferably, described rare gas element is the one in nitrogen and argon gas.
Preferably, described catalyzer is two (triphenylphosphine) palladium chloride (Pd (PPh 3) 2cl 2), tetrakis triphenylphosphine palladium (Pd (PPh 3) 4) and three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in one.
Preferably, the mole dosage of described catalyzer is 0.01% ~ 5% of compound j mole dosage, for three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture, three (dibenzalacetone) two palladium (Pd 2(dba) 3) mole dosage be 0.01% ~ 5% of compound j mole dosage.Preferably, described three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mixture in, three (dibenzalacetone) two palladium (Pd 2(dba) 3) and tri-o-tolyl phosphine (P (o-Tol) 3) mol ratio be 1:2 ~ 1:20.
IV, in atmosphere of inert gases, compound n is added in anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution of n-Butyl Lithium (n-BuLi), n-Butyl Lithium (n-BuLi): the mol ratio of compound n is 2.2:1 ~ 2.5:1, finish, at-78 ℃, after stirring reaction 2h, add trimethyltin chloride (Me 3snCl), trimethyltin chloride (Me 3snCl): mol ratio 2:1 ~ 2.5:1 of compound n, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain compd B, reaction formula is:
Figure BDA00002482100300091
Preferably, described rare gas element is the one in nitrogen and argon gas.
Preferably, described n-Butyl Lithium (n-BuLi): the mol ratio of compound n is 2.5:1.Preferably, described trimethyltin chloride (Me 3snCl): the mol ratio 2.5:1 of compound n.
Wherein, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl.
In embodiment below, for convenience of statement, the compd B of different substituents is used respectively B1, B2, B3, B4, B5 etc. represent, intermediate reaction thing and product also according to said method represent, the compound f f1 of for example different substituents, f2, f3 etc. represent, name and are as the criterion with the title in each embodiment.
The third aspect, the invention provides a kind of application containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, is described containing the application of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers in polymer solar cell device, organic electroluminescence device and organic field effect tube.Described Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers that contain are as described in first aspect present invention.
One provided by the invention, containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers and preparation method thereof and application, has following beneficial effect:
Of the present inventionly in polymer backbone, introduce Thienopyrroles diketone and be subject to body unit and dibenzothiophene benzene 1,4-Dithiapentalene to body unit containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, by giving " push away-La electronics " between acceptor effect, reduce the energy gap of polymkeric substance, the absorption band of polymkeric substance is moved to infrared and near infrared low energy wave band, widen the light abstraction width of polymkeric substance, make its absorption spectrum generation red shift, high with the matching degree of solar spectrum, carrier mobility speed improves, and effciency of energy transfer is also improved.
There is no at present bibliographical information and related application openly containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, it is a kind of new photoelectric material, effciency of energy transfer is high, preparation method is simple, productive rate is high, mild condition, product is easy to control, and makes its having a extensive future in field of photovoltaic materials such as polymer solar batteries.
Accompanying drawing explanation
Fig. 1 is the structural representation of the polymer solar cell device of embodiment 9.
Fig. 2 is the structural representation of the organic electroluminescence device of embodiment 10.
Fig. 3 is the structural representation of the organic field effect tube of embodiment 11.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
The present invention relates to containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, for thering is the polymer P of following general formula:
P:
Figure BDA00002482100300101
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is:
Figure BDA00002482100300102
r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
Alkyl in polymer architecture prepared by following examples, except particularly pointing out, is the alkyl of linear chain structure, for example-C 10h 21for positive certain herbaceous plants with big flowers base, be called for short certain herbaceous plants with big flowers base.
Embodiment 1
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-, bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 1, wherein, n=80:
P1：
Figure BDA00002482100300111
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A1) is as follows:
Figure BDA00002482100300112
Concrete operations are as follows:
(1) prepare 4,5-, bis-certain herbaceous plants with big flowers base-2,7-tin trimethyl benzo [2,1-b:3,4-b '] two thiophene (b1):
In nitrogen atmosphere by 2.36g (5mmol) 4, 5-bis-certain herbaceous plants with big flowers base benzos [2, 1-b:3, 4-b '] two thiophene (a1) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, stirring reaction 2h at-78 ℃, add the trimethyltin chloride (12.5mmol) of 3.7mL, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-certain herbaceous plants with big flowers base-2, 7-tin trimethyl benzo [2, 1-b:3, 4-b '] two thiophene (b1), mass spectrometric measurement data are MS (EI) m/z:796 (M+).
(2) prepare 4,5-, bis-certain herbaceous plants with big flowers base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d1):
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 1.22g (1.53mmol) 4,5-bis-certain herbaceous plants with big flowers base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b1) add in 30mL dry DMF, logical nitrogen bubble 30min, adds rapidly 0.087g (0.075mmol) Pd (PPh 3) 4, be heated to 80 ℃ of stirring reaction 24h, after stopped reaction, remove excessive DMF under reduced pressure, residue is dissolved by ethyl acetate, and Potassium monofluoride (KF) aqueous solution that is 10% with massfraction washes, through MgSO 4after dry, filter, revolve steaming, the normal hexane/tetrahydrofuran (THF) mixed solvent take volume ratio as 3:1, as elutriant is through silica gel column chromatography column separating purification, obtains 4,5-bis-certain herbaceous plants with big flowers base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d1), productive rate is 82%, and mass spectrometric measurement data are MS (EI) m/z:747 (M+);
(3) prepare 7,8-, bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e1):
By 0.22g (0.3mmol) 4; 5-bis-certain herbaceous plants with big flowers base-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d1) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; after vacuum-drying, join in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 7,8-, bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzos [2,1-b:3,4-b '] two thiophene (e1), productive rate 63%, mass spectrometric measurement data are MS (MALDI) m/z:683 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.94g (4.31mmol) 7, 8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e1) add in 60mL DMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding anhydrous magnesium sulfate drying filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 5:1 is elutriant again, carry out separating-purifying with silica gel column chromatography, obtain 4, 11-bis-bromo-7, 8-bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A1), productive rate is 71%.
The mass spectrometric measurement result of compd A 1 is MS (MALDI) m/z:841 (M+);
The structural analysis data of compd A 1 are: 1h NMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.55 (t, J=7.13Hz, 4H), 1.62-1.29 (m, 32H), 0.93-0.84 (t, J=13.44Hz, 6H).
Two, prepare compound B-11, wherein-C 8h 17for n-octyl, reaction scheme is as follows:
Specifically comprise the following steps:
I, 5-thiotolene also [3, 4-c] pyrroles-4, the preparation method of 6-diketone (i1) comprises the following steps: by 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 ℃, stirring reaction 12h, be cooled to room temperature, remove reaction solution, be precipitated, for the crude product of compound g, gained crude product is dissolved with 50mL toluene, add 0.24g (7.5mmol) methylamine (h1), be heated to 110 ℃ of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, be heated to after 80 ℃ of stirring and refluxing 4h cooling, remove thionyl chloride under reduced pressure, methylene dichloride/sherwood oil mixed solvent take volume ratio as 3:2 is elutriant, carry out separating-purifying with silica gel column chromatography, 5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (i1), productive rate 56%.
II, preparation also [3,4-c] pyrroles-4 of the bromo-5-thiotolene of 1,3-bis-, 6-diketone (j 1):
By 1.67g (10mmol) 5-thiotolene also [3,4-c] pyrroles-4,6-diketone (i1) is dissolved in the mixed solution of the 10mL vitriol oil (mass concentration is 98%, lower same) and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is joined in reaction flask for four times, under room temperature, stirring reaction spends the night, and reaction solution is poured in distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, and the methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain the bromo-5-thiotolene of 1,3-bis-also [3,4-c] pyrroles-4,6-diketone (j1), productive rate 80%.
III, preparation also [3,4-c] pyrroles-4 of 1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene, 6-diketone (n1):
Under nitrogen protection; by 0.84g (5mmol) 1; the bromo-5-thiotolene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j1) and 3.59g (10mmol) 4-octyl group-2-tin trimethyl thiophene (k1) add in tetrahydrofuran (THF) successively; logical nitrogen bubble 0.5h removes residual oxygen, then adds rapidly 0.11g (0.15mmol) catalyst P d (PPh 3) 2cl 2, logical nitrogen bubble 1h removes residual oxygen, in 60 ℃ of stirring and refluxing reaction 24h, is cooled to room temperature, and reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, uses anhydrous MgSO 4dried overnight, filter, revolve and steam except chloroform, methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 1,3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n1).
IV, preparation 1,3-bis-(4-octyl group-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone (B1):
Under nitrogen protection, by 2.78g (5mmol) 1, 3-bis-(4-octyl group-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (n1) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.7mL (12.5mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 1, 3-bis-(4-octyl group-5-tin trimethyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (B1), mass spectrometric measurement data are MS (MALDI) m/z:881 (M+).
Three, poly-{ 7,8-, bis-certain herbaceous plants with big flowers base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1, also [3,4-c] pyrroles-4 of 3-bis-(4-octyl group-2-thiophene)-5-thiotolene, 6-diketone }, the preparation method of polymer P 1 comprises following operation steps:
Under nitrogen protection; 1.68g (2.0mmol) compd A 1 and 1.76g (2.0mmol) compound B-11 are added in the toluene that 30mL is dry; logical nitrogen bubble 0.25h removes residual oxygen, then adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, logical nitrogen bubble 1h removes residual oxygen, is heated to 120 ℃ of back flow reaction 24h, remove reaction solution under reduced pressure toluene, surplus materials is added drop-wise to and in methyl alcohol, carries out sedimentation, suction filtration, with dry after methanol wash, then carry out separating-purifying take chloroform as elutriant with alumina chromatographic column, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 1, reaction formula is:
Figure BDA00002482100300151
Polymer P 1 is carried out to GPC test, and moving phase is THF, records Mn=89760, Mw/Mn=1.8, n=80.
Embodiment 2
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 2, wherein, n=45:
P2：
Figure BDA00002482100300161
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A2) is as follows:
Figure BDA00002482100300171
Concrete operations are as follows:
(1) prepare 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b2):
In nitrogen atmosphere by 1.93g (5mmol) 4, 5-bis-(2-ethyl pentyl group) benzo [2, 1-b:3, 4-b '] two thiophene (a2) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 ℃ after stirring reaction 2h, add again the trimethyltin chloride of 3.3mL (11mmol), after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-(2-ethyl pentyl group)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b2), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) prepare 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d2):
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 0.96g (1.34mmol) 4,5-bis-(2-ethyl pentyl group)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b2) add in the tetrahydrofuran (THF) that 30mL is dry, logical nitrogen bubble 30min, adds rapidly 0.047g (0.067mmol) Pd (PPh 3) 2cl 2, be heated to 60 ℃ of stirring reaction 48h, after stopped reaction, remove excessive DMF under reduced pressure, reaction residues is dissolved by ethyl acetate, and wash with 10% the KF aqueous solution, through MgSO 4after dry; filter; revolve steaming, the mixed solvent of the normal hexane/tetrahydrofuran (THF) take volume ratio as 1:3, as elutriant is through silica gel column chromatography column separating purification, obtains 4; 5-bis-(2-ethyl pentyl group)-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d2); productive rate is 79%, and mass spectrometric measurement data are MS (EI) m/z:663 (M+);
(3) prepare 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e2), comprise the following steps:
By 0.66g (1mmol) 4; 5-bis-(2-ethyl pentyl group)-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d2) and 0.071g (0.5mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; after vacuum-drying, join in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e2), productive rate is 76%
Mass spectrometric measurement data are MS (MALDI) m/z:599 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.46g (4.31mmol) 7, 8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e2) add in 60mL DMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding anhydrous magnesium sulfate drying filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 4, 11-bis-bromo-7, 8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A2),
The mass spectrometric measurement data of compd A 2 are MS (MALDI) m/z:757 (M+);
The hydrogen spectrum analysis data of compd A 2 are: 1h NMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.76 (m, 1H), 1.62-1.29 (m, 16H), 0.91 (tt, J=13.44,6.74,6.74Hz, 9H).
Two, preparation 1,3-bis-(5-tin trimethyl-2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4, the reaction scheme of 6-diketone (B2) is as follows:
Figure BDA00002482100300191
Comprise following operation steps:
I, preparation 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (i2):
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 ℃, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product is dissolved with 50mL toluene, add 1.28g (6.0mmol) 3-butyl certain herbaceous plants with big flowers amine (h2), be heated to 110 ℃ of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, be heated to after 80 ℃ of stirring and refluxing 4h cooling, remove thionyl chloride under reduced pressure, methylene dichloride/sherwood oil mixed solvent take volume ratio as 3:2 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3, 4-c] pyrroles-4, 6-diketone (i2), productive rate 54%.
II, preparation 1,3-bis-bromo-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (j2):
By 3.50g (10mmol) 5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (i2) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is added for four times in the single port bottle of 150mL, stirring at room temperature reaction is spent the night, reaction solution is poured in distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves to steam and removes chloroform, and the methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is elutriant, through silica gel column chromatography column separating purification, obtain the bromo-5-of 1,3-bis-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (j2).
III, preparation 1,3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (n2):
Under nitrogen protection; by 2.54g (5mmol) 1; the bromo-5-of 3-bis-(3-butyl) certain herbaceous plants with big flowers base thieno-[3; 4-c] pyrroles-4; 6-diketone (j2) and 3.09g (12.5mmol) 2-tin trimethyl thiophene (k2) add in tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds rapidly 0.35mg (0.0005mmol) Pd (PPh 3) 2cl 2, bubbling 1h removes residual oxygen, in 60 ℃ of stirring and refluxing reaction 24h, is cooled to room temperature, and reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, uses anhydrous MgSO 4dried overnight, filter, revolve to steam and remove chloroform, methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1.5 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 1,3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3,4-c] pyrroles-4,6-diketone (n2).
IV, under nitrogen protection, by 2.57g (5mmol) 1, 3-bis-(2-thiophene)-5-(3-butyl) certain herbaceous plants with big flowers base thieno-[3, 4-c] pyrroles-4, 6-diketone (n2) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.3mL (11mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 1, 3-bis-(5-tin trimethyl-2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3, 4-c] pyrroles-4, 6-diketone (B2), the mass spectrometric measurement data of compd B 2 are MS (MALDI) m/z:839 (M+).
Three, poly-{ 7,8-bis-(2-ethyl pentyl group) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(2-thiophene)-5-(3-butyl certain herbaceous plants with big flowers base) thieno-[3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 2 comprises following operation steps:
Under nitrogen protection; 1.51g (2.0mmol) compd A 2 and 2.52g (3.0mmol) compd B 2 are added in 30ml tetrahydrofuran (THF); bubbling 0.5h removes residual oxygen, adds rapidly 0.14mg (0.0002mmol) Pd (PPh 3) 2cl 2bubbling 1h removes residual oxygen, be heated to 60 ℃ of back flow reaction 48h, remove reaction solution under reduced pressure excessive tetrahydrofuran (THF), surplus materials is added drop-wise in methyl alcohol and carries out sedimentation, and suction filtration, with dry after methanol wash, then with alumina chromatographic column, dried surplus materials is carried out to separating-purifying take chloroform as elutriant, steam except organic solvent again, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 2, reaction formula is as follows:
Figure BDA00002482100300211
Polymer P 2 is carried out to GPC test, and moving phase is THF, records Mn=49860, Mw/Mn=1.9, n=45.
Embodiment 3
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 3, wherein, n=1:
P3：
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A3) is as follows:
Figure BDA00002482100300231
Specifically comprise the following steps:
(1) prepare 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b3):
In nitrogen atmosphere by 2.62g (5mmol) 4, 5-bis-(5-hexyl-2-thiophene) benzo [2, 1-b:3, 4-b '] two thiophene (a3) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.6mL (12mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-(5-hexyl-2-thiophene)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b3), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) prepare 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d3):
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.70g (2.0mmol) 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b3) add in the toluene that 30mL is dry, logical nitrogen bubble 30min, adds rapidly Pd 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.061g, 0.2mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 5% of compound b3, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, is heated to 110 ℃ of stirring reaction 48h, after stopped reaction, removes toluene under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter, revolve steaming, the normal hexane/tetrahydrofuran (THF) mixed solvent take volume ratio as 3:1 is elutriant; with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification; obtain 4,5-bis-(5-hexyl-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d3), productive rate 81%, mass spectrometric measurement data are MS (EI) m/z:635 (M+).
(3) prepare 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e3), comprise the following steps:
By 0.32g (0.40mmol) 4; 5-bis-(5-hexyl-2-thiophene)-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d3) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; after vacuum-drying, join in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e3), productive rate 73%, mass spectrometric measurement data are MS (MALDI) m/z:735 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 3.17g (4.31mmol) 7, 8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e3) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 4, 11-bis-bromo-7, 8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A3), productive rate 68%.
The mass spectrometric measurement data of compound A-13 are MS (MALDI) m/z:893 (M+);
The hydrogen spectrum analysis data of compound A-13 are: 1h NMR (300MHz, CD 2cl 2): δ (ppm)=7.95 (s, 2H), 7.82 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 6.67 (d, J=13.44Hz, 4H), 2.56 (t, J=6.34Hz, 4H), 1.62-1.29 (m, 16H), 0.93 (dt, J=6.74,6.74Hz, 6H).
Two, preparation 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, the reaction scheme of 6-diketone (B3) is:
Figure BDA00002482100300251
Specifically comprise following operation steps:
I, preparation also [3,4-c] pyrroles-4 of 5-hexyl thiophene, 6-diketone (i3):
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 ℃, stirring reaction 12h, be cooled to room temperature, remove reaction solution, be precipitated, for the crude product of compound g, gained crude product is dissolved with 50mL toluene, add 0.71g (7.0mmol) hexylamine (h3), be heated to 120 ℃ of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, be heated to after 80 ℃ of stirring and refluxing 4h cooling, remove thionyl chloride under reduced pressure, methylene dichloride/sherwood oil mixed solvent take volume ratio as 2:3 is elutriant, the surplus materials revolving after steaming is carried out to separation and purification with silica gel column chromatography, obtain 5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (i3), productive rate 51%.
II, preparation also [3,4-c] pyrroles-4 of the bromo-5-hexyl thiophene of 1,3-bis-, 6-diketone (j3):
By 2.37g (10mmol) 5-hexyl base thieno-[3,4-c] pyrroles-4,6-diketone (i3) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide is divided and joined in reaction flask for four times, under room temperature, stirring reaction spends the night, reaction solution is poured in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, and the methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain also [3,4-c] pyrroles-4 of the bromo-5-hexyl thiophene of 1,3-bis-, 6-diketone (j3).
III, preparation also [3,4-c] pyrroles-4 of 1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene, 6-diketone (n3):
Under nitrogen protection; by 1.98g (5mmol) 1; the bromo-5-hexyl thiophene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j3) and 4.57g (11mmol) 3-dodecyl-2-tin trimethyl thiophene (k3) add in tetrahydrofuran (THF) successively; logical nitrogen bubble 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.23g, 0.25mmol) and P (o-Tol) 3the mixture of (0.15g, 0.5mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 5% of compound j3, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, and logical nitrogen bubble 1h removes residual oxygen, in 60 ℃ of stirring and refluxing reaction 24h, is cooled to room temperature, and reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, uses anhydrous MgSO 4dried overnight, filter, revolve and steam except chloroform, methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (n3).
IV, preparation 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (B3):
Under nitrogen protection, by 3.69g (5mmol) 1, 3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (n3) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.6mL (12mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 1, 3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (B3), structure mass spectrometric measurement data are MS (MALDI) m/z:1064 (M+).
Three, poly-{ 7,8-bis-(5-hexyl-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 3 comprises the following steps:
Under nitrogen protection, 1.79g (2.0mmol) compound A-13 and 2.34g (2.2mmol) compd B 3 are added in 30mL DMF, bubbling 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.06g, 0.066mmol) and P (o-Tol) 3the mixture of (0.04g, 0.132mmol) is as catalyzer, Pd 2(dba) 3amount of substance be compound A-13 3.3%, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, bubbling 1h removes residual oxygen, be heated to 80 ℃ of back flow reaction 72h, remove reaction solution under reduced pressure DMF, be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, carry out separating-purifying take chloroform as elutriant with alumina chromatographic column, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 3, polymer P 3 is carried out to GPC test, moving phase is THF, record Mn=1469, Mw/Mn=2.3, n=1, reaction formula is as follows:
Figure BDA00002482100300281
Embodiment 4
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 4, wherein, n=65:
P4：
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A4) is as follows:
Figure BDA00002482100300291
Concrete operations are as follows:
(1) prepare 4,5-, bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b4):
In nitrogen atmosphere, by 2.52g (5mmol) 4, 5-bis-certain herbaceous plants with big flowers oxygen base benzos [2, 1-b:3, 4-b '] two thiophene (a4) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, stirring reaction 2h at-78 ℃, add 3.0mL (10mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-certain herbaceous plants with big flowers oxygen base-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b4), mass spectrometric measurement data are MS (EI) m/z:712 (M+).
(2) prepare 4,5-, bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d4):
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 2.07g (2.5mmol) 4,5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b4) add in 30mL dry DMF, and logical nitrogen bubble 30min, adds rapidly Pd 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.61g, 1.0mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 4% of compound b4, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, is heated to 80 ℃ of stirring reaction 48h, after stopped reaction, removes excessive DMF under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter; revolve steaming, the tetrahydrofuran (THF)/normal hexane mixed solvent take volume ratio as 1:3 is elutriant, carries out separation and purification with silica gel column chromatography; obtain 4; 5-bis-certain herbaceous plants with big flowers oxygen base-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3; 4-b '] two thiophene (d4), mass spectrometric measurement data are MS (EI) m/z:779 (M+).
(3) prepare 7,8-, bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e4):
By 0.39g (0.5mmol) 4; 5-bis-certain herbaceous plants with big flowers oxygen base-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d4) and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES add in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; pour reaction mixture in 100mL ice-water bath cancellation reaction, precipitated in a large number, filter; after vacuum-drying, add in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 carries out separating-purifying with silica gel column chromatography as elutriant, obtain 7,8-bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e4), mass spectrometry results is MS (MALDI) m/z:715 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 4.08g (4.31mmol) 7, 8-bis-certain herbaceous plants with big flowers oxygen base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e4) add in 60mL DMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 carries out separation and purification with silica gel column chromatography as elutriant, obtain 4, 11-bis-bromo-7, 8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A4).
The mass spectrometric measurement data of compd A 4 are: MS (MALDI) m/z:873 (M+); The hydrogen spectrum analysis data of compd A 4 are: 1h NMR (300MHz, CD 2cl 2), δ (ppm)=7.92 (s, 2H), 7.83 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 3.94 (t, J=13.44Hz, 4H), 1.72-1.29 (m, 32H), 0.96 (t, J=6.74,6H).
Two, preparation 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, the reaction scheme of 6-diketone (B4) is:
Figure BDA00002482100300311
Specifically comprise the following steps:
I, preparation also [3,4-c] pyrroles-4 of 5-hexyl thiophene, 6-diketone (i4):
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 ℃, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product is dissolved with 50mL toluene, add 0.66g (6.5mmol) hexylamine (h4), be heated to 120 ℃ of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, be heated to after 80 ℃ of stirring and refluxing 4h cooling, remove thionyl chloride under reduced pressure, methylene dichloride/sherwood oil mixed solvent take volume ratio as 3:2 carries out separating-purifying with silica gel column chromatography as elutriant, obtain 5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (i4), productive rate 56%.
II, preparation 1, the bromo-5-hexyl thiophene of 3-bis-also [3,4-c] pyrroles-4,6-diketone (j4): by 2.37g (10mmol) 5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone (i4) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is joined in reaction flask for four times, under room temperature, stirring reaction spends the night, and reaction solution is poured in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, take volume ratio as methylene dichloride/sherwood oil mixed solvent of 1: 1 is as elutriant, carries out separation and purification with silica gel column chromatography, obtains also [3,4-c] pyrroles-4 of the bromo-5-hexyl thiophene of 1,3-bis-, 6-diketone (j4).
III, preparation 1,3-bis-(3-hexyl-4-ethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (n4):
Under nitrogen protection; by 1.98g (5mmol) 1; the bromo-5-hexyl thiophene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j4) and 3.59g (10mmol) 3-hexyl-4-ethyl-2-tin trimethyl thiophene (k4) add in tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.14g, 0.15mmol) and P (o-Tol) 3the mixture of (0.46g, 1.5mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 3% of compound j4, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, and bubbling 1h removes residual oxygen, is warming up to 60 ℃ of stirring and refluxing reaction 24h, is cooled to room temperature, and reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, uses anhydrous MgSO 4dried overnight, filter, revolve to steam and remove chloroform, methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 carries out separation and purification with silica gel column chromatography as elutriant, obtain 1,3-bis-(3-hexyl-4-ethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (n4), productive rate is 71%.
IV, preparation 1,3-bis-(3-hexyl-4-ethyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (B4):
Under nitrogen protection, by 3.13g (5mmol) 1, 3-bis-(hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (n4) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.0mL (10mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 1, 3-bis-(3-hexyl-4-ethyl-5-tin trimethyl-2-thiophene)-5-hexyl thiophene also [3, 4-c] pyrroles-4, 6-diketone (B4), mass spectrometric measurement data are MS (MALDI) m/z:952 (M+).
Three, poly-{ 7,8-didecyl oxygen base dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-hexyl-4-ethyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 4 comprises the following steps:
Under nitrogen protection, 1.75g (2.0mmol) compd A 4 and 1.90g (2.0mmol) B4 are added in 30mL toluene, bubbling 0.5h removes residual oxygen, adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, bubbling 1h removes residual oxygen, is heated to 120 ℃ of back flow reaction 48h, remove reaction solution under reduced pressure toluene, be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, carry out separating-purifying take chloroform as elutriant with alumina chromatographic column, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 4, reaction formula is as follows:
Figure BDA00002482100300331
Polymer P 4 is carried out to GPC test, and moving phase is THF, records Mn=86905, Mw/Mn=1.7, n=65.
Embodiment 5
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone }, have following logical, be designated as polymer P 5, wherein, n=25:
P5：
Preparation method comprises the following steps:
One, the reaction scheme of preparation 4,11-dibromo dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A5):
Figure BDA00002482100300342
Concrete operations are as follows:
(1) prepare 2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b5):
In nitrogen atmosphere, by 0.95g (5mmol) benzo [2, 1-b:3, 4-b '] two thiophene (a5) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.7mL (12.5mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b5), mass spectrometric measurement data are MS (EI) m/z:516 (M+).
(2) prepare 2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d5):
By 1.1g (5mmol) 2-brooethyl thionyl benzene (c), 1.29g (2.5mmol) 2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b5) add in 30mL dry DMF, logical nitrogen bubble 30min, adds rapidly Pd 2(dba) 3(0.069g, 0.075mmol) and P (o-Tol) 3the mixture of (0.46g, 1.5mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 3% of compound b5, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, is heated to 80 ℃ of stirring reaction 48h, after stopped reaction, removes DMF under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter; revolve steaming; tetrahydrofuran (THF)/normal hexane solvent take volume ratio as 1:3 is as elutriant is through silica gel column chromatography column separating purification; obtain 2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3; 4-b '] two thiophene (d5), mass spectrometric measurement data are MS (EI) m/z:467 (M+);
(3) prepare dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e5):
By 0.17g (0.36mmol) 2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d5) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath; precipitated in a large number; filter, after vacuum-drying, join in 30mL pyridine, be heated to 110 ℃ of back flow reaction 12h; reaction solution is cooled to room temperature; add dichloromethane extraction, merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is as elutriant is through silica gel column chromatography column separating purification, obtain dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e5), mass spectrometric measurement data are MS (MALDI) m/z:403 (M+)
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 1.74g (4.31mmol) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e5) add in 60mL DMF, stirring at room temperature reaction 15h, is poured into water reaction solution, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, the ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5, as elutriant is through silica gel column chromatography column separating purification, obtains 4,11-dibromo dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A5).
The mass spectrometric measurement data of compound A-45 are MS (MALDI) m/z:560 (M+);
The hydrogen spectrum analysis data of compound A-45 are 1h NMR (300MHz, CD 2cl 2), δ (ppm)=8.03 (s, 2H), 7.67 (d, J=7.87Hz, 2H), 7.50 (d, J=7.83Hz, 2H).
Two, preparation 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, the reaction scheme of 6-diketone (B5) is as follows:
Figure BDA00002482100300361
Specifically comprise following operation steps:
I, preparation also [3,4-c] pyrroles-4 of 5-thiotolene, 6-diketone (i5):
By 0.86g (5mmol) thiophene-3, 4-dioctyl phthalate (f) adds in 25mL acetic anhydride, be heated to 140 ℃, stirring reaction 12h, be cooled to room temperature, remove reaction solution, obtain the crude product of compound g, gained crude product is dissolved with 50mL toluene, add 0.24g (7.5mmol) methylamine (h5), be heated to 110 ℃ of back flow reaction 24h, be cooled to room temperature, remove toluene under reduced pressure, with 50mL thionyl chloride, remaining solid thing in matrass is dissolved again, be heated to after 80 ℃ of stirring and refluxing 4h cooling, remove thionyl chloride under reduced pressure, methylene dichloride/sherwood oil mixed solvent take volume ratio as 2:3 is as elutriant is through silica gel column chromatography separating-purifying, obtain 5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (i5), productive rate 54%.
II, preparation also [3,4-c] pyrroles-4 of the bromo-5-thiotolene of 1,3-bis-, 6-diketone (j5):
By 1.67g (10mmol) 5-thiotolene also [3,4-c] pyrroles-4,6-diketone (i5) is dissolved in the mixed solution of the 10mL vitriol oil and 33mL trifluoroacetic acid, under lucifuge condition, 5.34g (30mmol) N-bromo-succinimide (NBS) point is joined in reaction flask for four times, under room temperature, stirring reaction spends the night, reaction solution is poured in appropriate distilled water, with chloroform extraction, merge organic phase, use anhydrous MgSO 4dried overnight, revolves except chloroform, and the methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1, as elutriant is through silica gel column chromatography column separating purification, obtains also [3,4-c] pyrroles-4 of the bromo-5-thiotolene of 1,3-bis-, 6-diketone (j5).
III, preparation 1,3-bis-(4-ethyl-3-hexyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone (n5):
Under nitrogen protection; by 1.63g (5mmol) 1; the bromo-5-thiotolene of 3-bis-also [3; 4-c] pyrroles-4; 6-diketone (j5) and 3.59g (10mmol) 3-hexyl-4-ethyl-2-tin trimethyl thiophene (k4) add in 80ml tetrahydrofuran (THF) successively; bubbling 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.14g, 0.15mmol) and P (o-Tol) 3the mixture of (0.92g, 3.0mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 3% of compound j5, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, and bubbling 1h removes residual oxygen, in 60 ℃ of stirring and refluxing reaction 24h, is cooled to room temperature, and reaction solution is poured into cancellation reaction in distilled water, with chloroform extraction, merges organic phase, uses anhydrous MgSO 4dried overnight, filters, and revolves to steam to remove chloroform, methylene dichloride/sherwood oil mixed solvent take volume ratio as 1:1 is as elutriant is through silica gel column chromatography column separating purification, obtains 1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone (n5), productive rate 69%.
IV, preparation 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone (B5):
Under nitrogen protection, by 2.78g (5mmol) 1, 3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (n5) adds in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.7mL (12.5mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 1, 3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene)-5-thiotolene also [3, 4-c] pyrroles-4, 6-diketone (B5), mass spectrometric measurement data are MS (MALDI) m/z:881 (M+).
Three, poly-{ dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone }, the preparation method of polymer P 5 comprises the following steps:
Under nitrogen protection, 1.12g (2.0mmol) compound A-45 and 1.76g (2.0mmol) compd B 5 are added in 30mLDMF, bubbling 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.3g, 1.0mmol) is as catalyzer, Pd 2(dba) 3amount of substance be compound A-45 5%, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, bubbling 1h removes residual oxygen, be heated to 80 ℃ of back flow reaction 48h, remove reaction solution under reduced pressure DMF, be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, then carry out separating-purifying take chloroform as eluent with alumina chromatographic column, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 5, polymer P 5 is carried out to GPC test, moving phase is THF, record Mn=14310, Mw/Mn=1.9, n=25, reaction formula is as follows:
Embodiment 6
A kind of containing diazosulfide-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 6, wherein, n=30:
P6：
Figure BDA00002482100300391
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, the reaction scheme of 8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A6):
Figure BDA00002482100300392
Concrete operations are as follows:
(1) prepare 4,5-dimethyl-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b6):
In nitrogen atmosphere, by 1.09g (5mmol) 4, 5-dimethylbiphenyl [2, 1-b:3, 4-b '] two thiophene (a6) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.5mL n-Butyl Lithium, 11.25mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.3mL (11mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-dimethyl-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b6), mass spectrometric measurement data are MS (EI) m/z:544 (M+).
(2) prepare 4,5-dimethyl-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d6):
By 0.74g (3.36mmol) 2-brooethyl thionyl benzene (c), 0.83g (1.53mmol) 4,5-dimethyl-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b6) add in 30mL anhydrous tetrahydro furan, logical nitrogen bubble 30min, adds rapidly 0.018mg (0.00015mmol) Pd (PPh 3) 4as catalyzer, be heated to 60 ℃ of stirring reaction 24h, after stopped reaction, remove tetrahydrofuran (THF) under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter; revolve steaming; tetrahydrofuran (THF)/normal hexane solvent take volume ratio as 1:3, as elutriant is through silica gel column chromatography column separating purification, obtains 4,5-dimethyl-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3,4-b '] two thiophene (d6), mass spectrometric measurement data are MS (EI) m/z:495 (M+);
(3) prepare 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e6):
By 0.20g (0.4mmol) 4; 5-dimethyl-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d6) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; after vacuum-drying, join in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is as elutriant is through silica gel column chromatography column separating purification, obtain 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e6), mass spectrometric measurement data are MS (MALDI) m/z:431 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 1.86g (4.31mmol) 7, 8-dimethyl dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e6) add in 60mL DMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 is elutriant, through silica gel column chromatography column separating purification, obtain 4, 11-bis-bromo-7, 8-dimethyl dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A6).
The mass spectrometric measurement data of compd A 6 are: MS (MALDI) m/z:588 (M+);
The hydrogen spectrum analysis data of compd A 6 are: 1h NMR (300MHz, CD 2cl 2): δ (ppm)=7.91 (s, 2H), 7.86 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 2.35 (s, 6H).
Two, preparation 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-thiotolene, 6-diketone (B5):
Preparation method is with embodiment 5 step 2.
Three, poly-{ 7,8-dimethyl dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-thiotolene also [3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 6 comprises the following steps:
Under nitrogen protection, 1.51g (2.0mmol) compd A 6 and 1.76g (2.0mmol) compd B 5 are added in 30mL tetrahydrofuran (THF), bubbling 0.5h removes residual oxygen, then adds rapidly 0.23mg (0.0002mmol) Pd (PPh 3) 4as catalyzer, bubbling 1h removes residual oxygen, be heated to 60 ℃ of back flow reaction 24h, remove reaction solution under reduced pressure tetrahydrofuran (THF), be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, then carry out separating-purifying take chloroform as eluent with alumina chromatographic column, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 6, polymer P 6 is carried out to GPC test, moving phase is THF, record Mn=29460, Mw/Mn=1.8, n=30, reaction formula is as follows:
Embodiment 7
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 7, wherein, n=20:
P7：
Figure BDA00002482100300421
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A7) is as follows:
Figure BDA00002482100300422
Specifically comprise the following steps:
(1) prepare 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b7):
In nitrogen atmosphere by 3.18g (5mmol) 4, 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) benzo [2, 1-b:3, 4-b '] two thiophene (a3) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 4.4mL n-Butyl Lithium, 11mmol), finish, at-78 ℃ after stirring reaction 2h, add again 3.6mL (12mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b7), mass spectrometric measurement data are MS (EI) m/z:961 (M+).
(2) prepare 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d7):
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.92g (2.0mmol) 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b7) add in the toluene that 30mL is dry, logical nitrogen bubble 30min, adds rapidly Pd 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.061g, 0.2mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 5% of compound b3, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:2, is heated to 110 ℃ of stirring reaction 48h, after stopped reaction, removes toluene under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter, revolve steaming, the normal hexane/tetrahydrofuran (THF) mixed solvent take volume ratio as 3:1 is elutriant; with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification; obtain 4,5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2,7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d7), productive rate 76%, mass spectrometric measurement data are MS (EI) m/z:911 (M+).
(3) prepare 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e7), comprise the following steps:
By 0.36g (0.40mmol) 4; 5-bis-(5-certain herbaceous plants with big flowers base-2-thiophene)-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d7) and 0.028g (0.2mmol) Vanadium Pentoxide in FLAKES join in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; then reaction mixture is poured into cancellation reaction in 100mL ice-water bath, precipitated in a large number, filter; after vacuum-drying, join in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e7), productive rate 70%, mass spectrometric measurement data are MS (MALDI) m/z:847 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 3.17g (4.31mmol) 7, 8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e7) add in 60mLDMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 is elutriant, with silica gel column chromatography to revolve steam after surplus materials carry out separation and purification, obtain 4, 11-bis-bromo-7, 8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A7), productive rate 68%.
The mass spectrometric measurement data of compd A 7 are MS (MALDI) m/z:1005 (M+);
The hydrogen spectrum analysis data of compd A 7 are: 1h NMR (300MHz, CD 2cl 2): δ (ppm)=7.95 (s, 2H), 7.82 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 6.67 (d, J=13.44Hz, 4H), 2.56 (t, J=6.34Hz, 4H), 1.62-1.29 (m, 32H), 0.93 (dt, J=6.74,6.74Hz, 6H).
Two, preparation 1,3-bis-(3-dodecyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (B3):
Preparation method is with embodiment 3 step 2.
Three, poly-{ 7,8-bis-(5-certain herbaceous plants with big flowers base-2-thiophene) dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(3-dodecyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 7 comprises the following steps:
Under nitrogen protection, 2.01g (2.0mmol) compd A 7 and 2.34g (2.2mmol) compd B 3 are added in 30mL DMF, bubbling 0.5h removes residual oxygen, then adds rapidly Pd 2(dba) 3(0.055g, 0.06mmol) and P (o-Tol) 3the mixture of (0.36g, 1.2mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 3% of compd A 7, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:20, bubbling 1h removes residual oxygen, be heated to 80 ℃ of back flow reaction 36h, remove reaction solution under reduced pressure DMF, be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, carry out separating-purifying take chloroform as elutriant with alumina chromatographic column, steam again except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 7, polymer P 7 is carried out to GPC test, moving phase is THF, record Mn=31640, Mw/Mn=2.3, n=20, reaction formula is as follows:
Embodiment 8
A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, be specially poly-{ 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, there is following general formula, be designated as polymer P 8, wherein, n=:
P8：
Figure BDA00002482100300452
Preparation method comprises the following steps:
One, preparation 4,11-bis-is bromo-7, and the reaction scheme of 8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (A8) is as follows:
Figure BDA00002482100300461
Concrete operations are as follows:
(1) prepare 4,5-dimethoxy-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b8):
In nitrogen atmosphere, by 1.40g (5mmol) 4, 5-dimethoxy benzo [2, 1-b:3, 4-b '] two thiophene (a8) add in 60mL anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution (2.5M of 5mL n-Butyl Lithium, 12.5mmol), finish, stirring reaction 2h at-78 ℃, add 3.6mL (12mmol) trimethyltin chloride, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain 4, 5-dimethoxy-2, 7-bis-(tin trimethyl) benzo [2, 1-b:3, 4-b '] two thiophene (b8), mass spectrometric measurement data are MS (EI) m/z:576 (M+).
(2) prepare 4,5-dimethoxy-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3,4-b '] two thiophene (d8):
By 1.1g (5.0mmol) 2-brooethyl thionyl benzene (c), 1.44g (2.5mmol) 4,5-dimethoxy-2,7-bis-(tin trimethyl) benzo [2,1-b:3,4-b '] two thiophene (b8) add in 30mL dry DMF, and logical nitrogen bubble 30min, adds rapidly Pd 2(dba) 3(0.092g, 0.1mmol) and P (o-Tol) 3the mixture of (0.61g, 1.0mmol) is as catalyzer, Pd 2(dba) 3amount of substance be 4% of compound b8, Pd 2(dba) 3with P (o-Tol) 3mol ratio is 1:10, is heated to 80 ℃ of stirring reaction 48h, after stopped reaction, removes excessive DMF under reduced pressure, reaction residues is dissolved by ethyl acetate, and the KF aqueous solution that is 10% with massfraction washes, through MgSO 4after dry; filter; revolve steaming, the tetrahydrofuran (THF)/normal hexane mixed solvent take volume ratio as 1:3 is elutriant, carries out separation and purification with silica gel column chromatography; obtain 4; 5-dimethoxy-2,7-bis-(2-methyl sulfinyl benzene) benzo [2,1-b:3; 4-b '] two thiophene (d8), mass spectrometric measurement data are MS (EI) m/z:527 (M+).
(3) prepare 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e8):
By 0.26g (0.5mmol) 4; 5-dimethoxy-2; 7-bis-(2-methyl sulfinyl benzene) benzo [2; 1-b:3; 4-b '] two thiophene (d8) and 0.036g (0.25mmol) Vanadium Pentoxide in FLAKES add in 6mL trifluoromethanesulfonic acid; stirring at room temperature reaction 72h; pour reaction mixture in 100mL ice-water bath cancellation reaction, precipitated in a large number, filter; after vacuum-drying, add in 30mL pyridine; be heated to 110 ℃ of back flow reaction 12h, reaction solution is cooled to room temperature, add dichloromethane extraction; merge organic phase, use anhydrous MgSO 4after dry, revolve steaming, methylene dichloride/normal hexane mixed solvent take volume ratio as 1:9 carries out separating-purifying with silica gel column chromatography as elutriant, obtain 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene (e8), mass spectrometry results is MS (MALDI) m/z:463 (M+).
(4) under lucifuge condition, by 2.31g (13.0mmol) NBS, 2.0g (4.31mmol) 7, 8-dimethoxy dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (e8) add in 60mL DMF, stirring at room temperature reaction 15h, reaction solution is poured into water, through washing, by extracted with diethyl ether, after adding dried over mgso filtration, revolve steaming, ethyl acetate/petroleum ether mixed solvent take volume ratio as 1:5 carries out separation and purification with silica gel column chromatography as elutriant, obtain 4, 11-bis-bromo-7, 8-dimethoxy dibenzo [b, b '] thiophene benzo [2, 1-b:3, 4-b '] two thiophene (A8).
The mass spectrometric measurement data of compound A-28 are: MS (MALDI) m/z:607 (M+);
The hydrogen spectrum analysis data of compound A-28 are: 1h NMR (300MHz, CD 2cl 2), δ (ppm)=7.92 (s, 2H), 7.83 (d, J=7.87Hz, 2H), 7.52 (d, J=7.83Hz, 2H), 3.74 (s, 6H).
Two, preparation 1,3-bis-(4-ethyl-3-hexyl-5-tin trimethyl-2-thiophene) also [3,4-c] pyrroles-4 of-5-hexyl thiophene, 6-diketone (B4):
Preparation method is with embodiment 4 step 2.
Three, poly-{ 7,8-dimethoxy dibenzo [b, b '] thiophene benzo [2,1-b:3,4-b '] two thiophene-co-1,3-bis-(4-ethyl-3-hexyl-2-thiophene)-5-hexyl thiophene also [3,4-c] pyrroles-4,6-diketone }, the preparation method of polymer P 8 comprises the following steps:
Under nitrogen protection, 1.21g (2.0mmol) compd A 4 and 1.90g (2.0mmol) B4 are added in 30mL toluene, bubbling 0.5h removes residual oxygen, adds rapidly 46mg (0.04mmol) Pd (PPh 3) 4, bubbling 1h removes residual oxygen, is heated to 120 ℃ of back flow reaction 48h, remove reaction solution under reduced pressure toluene, be added drop-wise to and in methyl alcohol, carry out sedimentation, suction filtration, with dry after methanol wash, carry out separating-purifying take chloroform as elutriant with alumina chromatographic column, then steam except organic solvent, use methyl alcohol sedimentation, suction filtration, gained solid extracts three days by acetone Soxhlet, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain polymer P 8, reaction formula is as follows:
Figure BDA00002482100300481
Polymer P 8 is carried out to GPC test, and moving phase is THF, records Mn=13020, Mw/Mn=1.7, n=12.
Embodiment 9
The material as active coating containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer P3 of preparing take the embodiment of the present invention 3, prepare organic solar cell device, its structure comprises the substrate of glass 1 stacking gradually, anode 2, middle supplementary layer 3, active coating 4 and negative electrode 5, this device architecture specifically can briefly be described as: substrate of glass/anode/middle supplementary layer/active coating/negative electrode, see Fig. 1.Wherein, anode 2 is ITO, that square resistance is the tin indium oxide of 15 Ω/mouths, for being attached to the functional layer of glass basic surface, be called ito glass together with substrate of glass, can buy, the material of middle supplementary layer 3 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, be called for short PEDOT:PSS(commodity CLEVIOS P VP Al 4083 by name); The material of active coating 4 comprises electron donor material and electron acceptor material, electron donor(ED) be the embodiment of the present invention 3 prepare containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer P3, electron acceptor(EA) is [6,6] phenyl-C61-methyl-butyrate (PCBM); The material of negative electrode 5 is aluminium.
Wherein, substrate of glass 1, as bottom, is chosen ito glass when making, and with ITO layer, as anode 2, ito glass thickness is 1.1mm, after ultrasonic cleaning, with oxygen plasma (oxygen-Plasma) processing; Then spin coating PEDOT:PSS on ito glass, supplementary layer 3 in the middle of preparing, thickness is 40nm; That prepared by the 10mg embodiment of the present invention is dissolved in 0.4ml dimethylbenzene and obtains solution 1 containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers again, getting 10mg PCBM is dissolved in 0.4ml chlorobenzene and obtains solution 2, solution 1 and solution 2 are spun on middle supplementary layer 3, obtain active coating 4, thickness is 120nm; Be 2 × 10 at pressure -4under the vacuum condition of Pa, evaporation metal aluminium obtains negative electrode 5, and thickness is 80nm, and all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided, and obtain organic solar batteries device.Contain the present invention and be not limited to the present embodiment containing preparation method and the structure of the organic solar batteries device of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, can device suitably be improved or be modified.
By the I-E characteristic of Keithley236 current/voltage source-measuring system test component, the open circuit voltage that records device is 0.52V, and packing factor is 41%, and short-circuit current density is 7.21mA/cm 2, energy conversion efficiency is 1.54%.
Embodiment 10
The polymer P 8 of preparing take embodiment 8 is the material of luminescent layer, be prepared with organic electroluminescence devices, its structure comprises the glass substrate 1 stacking gradually, transparent anode 2, luminescent layer 3, buffer layer 4, negative electrode 5, the structure of device is specially: glass substrate/transparent anode/luminescent layer/buffer layer/negative electrode, see Fig. 2.
Wherein, deposit the tin indium oxide that square resistance is 15 Ω/mouths (ITO) on glass substrate 1, thickness is 120nm, as transparent anode 2, on transparent anode, after spin coating one layer of polymeric P8, prepare luminescent layer 3, thickness is 80nm, buffer layer 4 is prepared in vacuum evaporation, and material is LiF, and thickness is 1nm, last evaporation is prepared negative electrode 5, material is metal A l, and thickness is 120nm, and the structure of practical devices is not limited to this.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 1.19cd/A, and high-high brightness is 917cd/m 2.
Embodiment 11
The polymer P 3 of preparing take the embodiment of the present invention 3, as the material of organic semiconductor layer, is prepared with field effect transistors, and its structure as shown in Figure 3, comprise the substrate 1 stacking gradually, insulation layer 2, decorative layer 3, organic semiconductor layer 4, source electrode (S) 5 and drain electrode (D) 6.Wherein, the material of substrate 1 is highly doped silicon chip (Si), and the material of insulation layer 2 can be but be not limited to the SiO that thickness is 450nm 2, the material of decorative layer 3 is octadecyl trichlorosilane alkane (OTS), and the material of organic semiconductor layer 4 is polymer P 3 prepared by the embodiment of the present invention 3, and the material of source electrode (S) 5 and drain electrode (D) 6 is aluminium.
In the preparation of above-mentioned organic field effect tube, the thickness of substrate 1 is 1mm, the thickness of insulation layer 2 is 450nm, the thickness of decorative layer 3 is 2nm, source electrode 5(S) thickness be 50nm, drain electrode 6(D) thickness be 50nm, all adopt and shelter deposition method preparation, the preparation of organic semiconductor layer is that polymer P 3 prepared by the embodiment of the present invention 3 is spun to the insulation layer SiO being modified by decorative layer octadecyl trichlorosilane alkane (OTS) 2upper, thickness is 2nm, obtains organic field effect tube.
By time of flight method (Time of Flight, TOF), 7.0 × 10 5vcm -1electric field in the mean void mobility of the test organic field effect tube that contains polymer P 3 prepared by the embodiment of the present invention 3 be 1.8 × 10 -4cm 2/ Vs, shows that the hole transport performance containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers prepared by the present invention is good.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, it is characterized in that, for thering is the polymer P of following general formula:
P:
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is: r ' is C 6~ C 10alkyl, n is the natural number between 1 ~ 80.
2. containing a preparation method for Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, it is characterized in that, comprise following operation steps:
Compd A and compd B are provided, and the structural formula of compd A and B is respectively:
Figure FDA00002482100200013
In formula, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl, the skeleton symbol of described alkylthrophene group is:
Figure FDA00002482100200014
r ' is C 6~ C 10alkyl;
Under protection of inert gas; compd A and compd B were added in organic solvent in 1: 1 in molar ratio ~ 1: 1.5; add catalyzer; carry out Stille coupling reaction 24 ~ 72 hours at 60 ~ 120 ℃; after separation and purification, obtain containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers, described is the polymer P with following general formula containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers:
P:
Figure FDA00002482100200021
In formula, n is the natural number between 1 ~ 80.
3. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 2, it is characterized in that, described catalyzer is the one in the mixture of two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium and three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine.
4. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 2, it is characterized in that, the mole dosage of described catalyzer is 0.01% ~ 5% of compd A mole dosage, for the mixture of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, the mole dosage of described three (dibenzalacetone) two palladiums is 0.01% ~ 5% of compd A mole dosage.
5. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 2, it is characterized in that, in the mixture of described three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, the mol ratio of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine is 1:2 ~ 1:20.
6. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 2, is characterized in that, the preparation method of described compd A comprises following operation steps:
(1) under protection of inert gas; compound a is added in tetrahydrofuran (THF), be cooled to-78 ℃, slowly add n-Butyl Lithium; the mol ratio of n-Butyl Lithium and compound a is 2.2:1 ~ 2.5:1; then stirring reaction 2h at-78 ℃, then add trimethyltin chloride, the mol ratio of trimethyltin chloride and compound a is 2:1 ~ 2.5:1; after insulation reaction 0.5h, return to room temperature; continue reaction 24h, obtain compound b, reaction formula is:
(2) under rare gas element and oxygen free condition, the compound b that is 1:2 ~ 1:2.5 by mol ratio and compound c 2-brooethyl thionyl benzene add in solvent, add catalyzer, at 80 ℃, Stille coupling reaction 48h occur, and obtain compound d, and reaction formula is:
Described catalyzer is the one in the mixture of two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium and three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine;
(3) in trifluoromethanesulfonic acid, after compound d reacts with Vanadium Pentoxide in FLAKES, pour reactant in ice-water bath cancellation reaction, be precipitated, gained precipitation is added in pyridine and carries out back flow reaction, obtain Verbindung, reaction formula is:
Figure FDA00002482100200041
Described reaction with Vanadium Pentoxide in FLAKES is at room temperature reaction 72h, and the mol ratio of described compound d and Vanadium Pentoxide in FLAKES is 1.5:1 ~ 2.0:1, and the temperature of described back flow reaction is 110 ℃, and the reaction times is 12h;
(4) under lucifuge condition, there is bromination reaction in N-bromo-succinimide and Verbindung, obtain compd A in dimethyl formamide, and reaction formula is:
Figure FDA00002482100200042
Described N-bromo-succinimide: the mol ratio of Verbindung is 3:1, described bromination reaction is at room temperature to react 15h;
Wherein, R 1, R 2for H, C 1~ C 10alkyl, C 1~ C 10alkoxyl group or alkylthrophene group, the skeleton symbol of described alkylthrophene group is:
Figure FDA00002482100200043
r ' is C 6~ C 10alkyl.
7. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 6, it is characterized in that, in step (2), the mole dosage of described catalyzer is 0.01% ~ 5% of compound b mole dosage, for the mixture of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, the mole dosage of three (dibenzalacetone) two palladiums is that 0.01% ~ 5%, three (dibenzalacetone) two palladiums of compound b mole dosage and the mol ratio of tri-o-tolyl phosphine are 1:2 ~ 1:20.
8. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 2, is characterized in that, the preparation method of described compd B comprises following operation steps:
I, compound f thiophene-3, there is condensation reaction in 4-dioctyl phthalate, obtain the crude product of compound g in acetic anhydride, and described crude product reacts with thionyl chloride after reacting with compound h again, obtains compound i, and reaction formula is:
Figure FDA00002482100200051
Described setting-up point is 140 ℃, and the time is 12h; Described compound f: the mol ratio of compound h is 1:1.2 ~ 1:1.5; Described and compound h temperature of reaction is 110 ℃, and the reaction times is 24h, and described temperature of reacting with thionyl chloride is 80 ℃, and the time is 4h;
Under II, lucifuge condition, in the mixed solution of sulfuric acid and trifluoroacetic acid formation, compound i at room temperature reacts and spends the night with N-bromo-succinimide, obtains compound j, and reaction formula is as follows:
Figure FDA00002482100200052
Described sulfuric acid is that massfraction is 98% the vitriol oil, and the mol ratio of described compound i:N-bromo-succinimide is 1:3, and described N-bromo-succinimide divides four times and adds;
III, in anaerobic and atmosphere of inert gases, compound j and compound k are added in tetrahydrofuran (THF) with mol ratio 1:2, add catalyzer, be heated to 60 ℃ and carry out Stille coupling reaction 24h, obtain compound n, reaction formula is:
Figure FDA00002482100200061
Described catalyzer is the one in the mixture of two (triphenylphosphine) palladium chloride, tetrakis triphenylphosphine palladium and three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine;
IV, in atmosphere of inert gases, compound n is added in anhydrous tetrahydro furan, be cooled to-78 ℃, slowly add the hexane solution of n-Butyl Lithium, n-Butyl Lithium: the mol ratio of compound n is 2.2:1 ~ 2.5:1, finishes, at-78 ℃ after stirring reaction 2h, add trimethyltin chloride, trimethyltin chloride: mol ratio 2:1 ~ 2.5:1 of compound n, after insulation reaction 0.5h, return to room temperature, continue reaction 24h, obtain compd B, reaction formula is:
Figure FDA00002482100200062
Wherein, R 3for C 1~ C 14alkyl, R 4, R 5for H or C 2~ C 12alkyl.
9. the preparation method containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers as claimed in claim 8, it is characterized in that, in step III, the mole dosage of described catalyzer is 0.01% ~ 5% of compound j mole dosage, for the mixture of three (dibenzalacetone) two palladiums and tri-o-tolyl phosphine, the mole dosage of three (dibenzalacetone) two palladiums is that 0.01% ~ 5%, three (dibenzalacetone) two palladiums of compound j mole dosage and the mol ratio of tri-o-tolyl phosphine are 1:2 ~ 1:20.
10. according to claim 1 containing the application of Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymers in polymer solar cell device, organic electroluminescence device or organic field effect tube.
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CN102344550A (en) * 2010-07-30 2012-02-08 海洋王照明科技股份有限公司 Perylenetetracarboxylic diimide copolymer containing thiophenepyrrole dione unit, preparation method thereof and application thereof

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CN111635507A (en) * 2020-06-15 2020-09-08 朱成杰 Blue-light organic electroluminescent material and preparation method thereof

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