CN103534246B

CN103534246B - A kind of photoelectric material and its production and use

Info

Publication number: CN103534246B
Application number: CN201280011939.7A
Authority: CN
Inventors: 陈永胜; 万相见; 刘永胜; 李智; 周娇艳; 王菲; 贺光瑞; 龙官奎
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2011-03-08
Filing date: 2012-03-07
Publication date: 2016-11-30
Anticipated expiration: 2032-03-07

Abstract

Disclose to receptor type oligo-thiophenes compound, its preparation method and purposes.

Description

A kind of photoelectric material and its production and use

Field

The application relates to technical field of material chemistry.More specifically, the application relates to field of photovoltaic materials

Background

Solar energy is that the mankind are inexhaustible, nexhaustible, the regenerative resource of cleanliness without any pollution.With inorganic solar cell Comparing, organic solar batteries has light weight, inexpensive, solution-processible, high mechanical flexibility, can be made into flexible broad area device Etc. advantage.

General introduction

On the one hand, the application relate to general formula to receptor type oligo-thiophenes compound:

Wherein, x is the integer of 0 to 50, and y is the integer of 1 to 50,

R₁And R₂Separately selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups Or the derivant of its halogen substiuted, wherein R₁And R₂Can be the same or different, but R₁And R₂Can not be H simultaneously,

L₁、L₂And L₃Separately selected from the conjugated electrons of the conjugated electrons donor monomer of bridging or bridging by body unit, And

A₂For end group by body unit.

On the other hand, the application relate to selected from formula (1) to formula (6) to receptor type oligo-thiophenes compound:

Wherein, n is the integer of 1 to 50,

D and D₁It is separately the conjugated electrons donor monomer of bridging,

A and A₁Be separately the conjugated electrons of bridging by body unit, and

A₂For end group by body unit.

On the other hand, the application relate to preparing formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes The method of compound, wherein, the oligo-thiophenes containing receptor end group of the donor bridging oligo-thiophenes by dialdehyde base donor bridging With receptor end monomers, in the presence of solvent and catalyst, carry out Ke Neifeinageer (Knoevenagel) condensation reaction, Obtain described compound.

Another further aspect, the application relates to preparing formula (1) to the side to receptor type oligo-thiophenes compound of formula (6) Method, wherein, the oligo-thiophenes containing small molecule dyes end group of donor bridging by the oligo-thiophenes of dialdehyde base donor bridging with have Machine small molecule dyes monomer, in the presence of solvent and catalyst, carries out Ke Neifeinageer (Knoevenagel) condensation anti- Should, obtain described compound.

Another aspect, the application relate to formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes chemical combination Thing purposes in preparing field-effect transistor.

On the other hand, the application relate to formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes chemical combination Thing purposes in preparing photovoltaic device.

Another further aspect, the application relate to comprising have formula (1) to formula (6) containing receptor end group to receptor type oligomerization The triode device of the active layer of thiophene compound.

Another aspect, the application relate to comprising have formula (1) to formula (6) containing receptor end group to receptor type oligomerization The photovoltaic device of the active layer of thiophene compound.

On the other hand, the application relates to the method preparing field-effect transistor, and it includes that offer has formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes compound.

Another further aspect, the application relates to the method preparing photovoltaic device, and it includes that offer has formula (1) to formula (6) Containing receptor end group to receptor type oligo-thiophenes compound.

Other aspects, the application relates to selected from following compound:

And

Accompanying drawing explanation

Fig. 1 is thermogravimetric analysis (TGA) curve of compound in the embodiment of the present application 2 and 3.

Fig. 2 is thermogravimetric analysis (TGA) curve of compound in the embodiment of the present application 4,5 and 6.

Fig. 3 is the cyclic voltammetry curve of compound in the embodiment of the present application 4,5 and 6.

Fig. 4 is the current density voltage curve of compound in the embodiment of the present application 4,5 and 6.

Fig. 5 shows the solution of compound and the ultraviolet-visible absorption spectroscopy of thin film in the embodiment of the present application 14.

Fig. 6 shows the solution of compound and the cyclic voltammetry curve of thin film in the embodiment of the present application 14.

Fig. 7 shows compound current density voltage curve under difference is to acceptor ratio in the embodiment of the present application 14.

Fig. 8 shows compound current density voltage curve under difference is to acceptor ratio in the embodiment of the present application 25.

Fig. 9 shows that in the embodiment of the present application 25, compound and C71PCBM add the electric current of PDMS under 1: 0.8 weight ratio Density-voltage curve.

Figure 10 shows compound and C in the embodiment of the present application 13₆₁PCBM is Current density-voltage under 1: 0.8 weight ratio Curve.

Figure 11 shows compound and C in the embodiment of the present application 17₆₁PCBM is Current density-voltage under 1: 0.8 weight ratio Curve.

Figure 12 shows compound and C in the embodiment of the present application 21₆₁PCBM is Current density-voltage under 1: 0.5 weight ratio Curve.

Figure 13 shows compound and C in the embodiment of the present application 23₆₁PCBM is Current density-voltage under 1: 0.8 weight ratio Curve.

Figure 14 shows compound and C in the embodiment of the present application 24₆₁PCBM Current density-voltage under Different Weight ratio is bent Line.

Figure 15 shows compound and C in the embodiment of the present application 27₆₁PCBM Current density-voltage under Different Weight ratio is bent Line.

Figure 16 shows compound and C in the embodiment of the present application 28₆₁PCBM is Current density-voltage under 1: 0.5 weight ratio Curve.

Figure 17 shows compound and C in the embodiment of the present application 29₆₁PCBM is Current density-voltage under 1: 0.8 weight ratio Curve.

Figure 18 shows compound and C in the embodiment of the present application 30₆₁PCBM is Current density-voltage under 1: 0.5 weight ratio Curve.

Figure 19 shows compound and C in the embodiment of the present application 34₆₁PCBM is Current density-voltage under 1: 0.5 weight ratio Curve.

Figure 20 shows compound and C in the embodiment of the present application 35₆₁PCBM is Current density-voltage under 1: 0.5 weight ratio Curve.

Describe in detail

In the following description, comprehensively reason is provided including some concrete details with embodiment disclosed in each Solve.But, those skilled in the relevant art are not it will be recognized that use these concrete details one or more, and use other Embodiment can be realized in the case of method, parts, material etc..

Unless required in addition that in the application, in entire disclosure and claims thereafter, word " includes " and " bag Contain " should be interpreted that open, to include formula meaning, i.e. " include but not limited to ".

" embodiment " that whole this specification is mentioned or " embodiment " or " in another embodiment " or " in certain embodiments " mean at least one embodiment include relevant to described in this embodiment with specific reference to Key element, structure or feature.Therefore, throughout the specification diverse location occur phrase " in one embodiment " or " in reality Execute in scheme " or " in another embodiment " or " in certain embodiments " same embodiment need not be all referred to.Additionally, Concrete key element, structure or feature can combine in any suitable manner in one or more embodiments.

Definition

By showing that the simplification symbol of the total number of carbon atoms found in shown chemical group is named herein above indicating Some chemical group.Such as, C₇-C₁₂Alkyl describes has the alkyl being defined below that sum is 7 to 12 carbon atoms, and C₄-C₁₂Cycloalkyl-alkyl describes has the cycloalkyl-alkyl being defined below that sum is 4 to 12 carbon atoms.Simplify carbon in symbol Total atom number does not comprise the carbon in the substituent group being likely to be present in described group.

Therefore, non-separately have a contrary explanation, otherwise in description and claims following term used have with Under the meaning:

In this application, term " alkyl " means and is made up of carbon and hydrogen atom, without unsaturated bond, has 1 to 30 Individual carbon atom, especially there is 1 to 12 carbon atom or 1 to 8 carbon atom, and by the remainder phase of singly-bound with molecule Straight or branched hydrocarbon chain radical even, such as methyl, ethyl, n-pro-pyl, 1-Methylethyl (isopropyl), normal-butyl, n-pentyl, 1,1-dimethyl ethyl (tert-butyl group), octyl group etc..

In certain embodiments, alkyl is C₁-C₃₀Alkyl.In certain embodiments, alkyl is C_1-C₁₂Alkyl.? In some embodiment, alkyl is C₁-C₈Alkyl.

Alkyl group can be the most substituted that is substituted or unsubstituted.When substituted, substituted radical is independent Ground and independently selected from following one or more groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alkoxyl, Aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamoyl, O-thiocarbamoyl, N-thiocarbamoyl, C-acylamino-, N-acylamino-, S-sulfonamido, N-sulfenyl ammonia Base, C-carboxyl, O-carboxyl, isocyanato-, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphonyl Base ,-NR ' R " or amino including single-and di-substituted amino group, and protected derivant.

In certain embodiments, C₁-C₃₀Alkyl is optionally substituted by halogen.

In this application, term " cycloalkyl " refers to only to be made up of carbon and hydrogen atom, has three to ten five carbon atoms, Especially there are 3 to 30 carbon atoms, and it is saturated, and steady with what the remainder of molecule was connected by singly-bound Fixed non-aromatic monocyclic or bicyclic hydrocarbon radical, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, ring decyl etc..

In certain embodiments, cycloalkyl is C₃-C₃₀Cycloalkyl.In certain embodiments, cycloalkyl is C₃-C₁₂Ring Alkyl.In certain embodiments, cycloalkyl is C₃-C₈Cycloalkyl.

Group of naphthene base can be the most substituted that is substituted or unsubstituted.When substituted, substituted radical is single Solely and independently selected from following one or more groups: cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxyl, alcoxyl Base, aryloxy group, sulfydryl, alkylthio group, arylthio, cyano group, halo, carbonyl, thiocarbonyl, O-carbamoyl, N-carbamyl Base, O-thiocarbamoyl, N-thiocarbamoyl, C-acylamino-, N-acylamino-, S-sulfonamido, N-sulfenyl Amino, C-carboxyl, O-carboxyl, the conjunction of Carbimide. armpit, thiocyano, isothiocyanato, nitro, silicyl, three halide sulphurs Acyl group ,-NR ' R " or amino including single-and di-substituted amino group, and protected derivant.

In certain embodiments, C₃-C₃₀Cycloalkyl is optionally substituted by halogen.

In this application, term " alkoxyl " refers to formula-OR, and wherein R is alkyl defined above, as methoxyl group, Ethyoxyl, positive propoxy, 1-methyl ethoxy (isopropoxy), n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta Epoxide, tertiary amoxy etc..The moieties of alkoxy base can be as at random taken as abovementioned alkyl group definition Generation.

In certain embodiments, alkoxyl is C₁-C₃₀Alkoxyl.In certain embodiments, alkoxyl is C₁-C₁₂Alkane Epoxide.In certain embodiments, alkoxyl is C₁-C₈Alkoxyl.

In certain embodiments, C₁-C₃₀Alkoxyl is optionally substituted by halogen.

In this application, term " carboxylic acid ester groups " refer to general formula R C (=O) OR '-, wherein R is alkyl or hydrogen, and R ' is hydrocarbon Base.

In certain embodiments, carboxylic acid ester groups is C₁-C₃₀Carboxylic acid ester groups.In certain embodiments, carboxylic acid ester groups is C₁-C₁₂Carboxylic acid ester groups.In certain embodiments, carboxylic acid ester groups is C₁-C₈Carboxylic acid ester groups.

In this application, term " halogen " means bromine, chlorine, fluorine or iodine.

In this application, term " receptor " means the molecule with electron acceptability.

In this application, term " conjugated electrons donor " means that having electronics gives the conjugated molecule of ability.

In this application, term " conjugated electrons receptor " means the conjugated molecule with electron acceptability.

In this application, term " organic molecule dyestuff " mean can by fiber or other substance stain in visible region There is the relatively strong organic micromolecule compound absorbed.

Detailed description of the invention

Wherein, x is the integer of 0 to 50, and y is the integer of 1 to 50,

A₂For end group by body unit.

Wherein, n is the integer of 1 to 50,

R₁And R₂Separately selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C_1-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups Or the derivant of its halogen substiuted, wherein R₁And R₂Can be the same or different, but R₁And R₂Can not be H simultaneously,

D and D₁It is separately the conjugated electrons donor monomer of bridging,

A and A₁Be separately the conjugated electrons of bridging by body unit, and

A₂For end group by body unit.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes D and D in compound₁Separately selected from group 7 to group 20:

Wherein R₃Selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or its halogen take The derivant in generation.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes A and A in compound₁Separately selected from group 21 to group 30:

Wherein R₄Selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or its halogen substiuted Derivant.

In certain embodiments, described formula (1) to formula (6) close receptor end group to receptor type oligo-thiophenes A in compound₂For organic molecule dye groups.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes A in compound₂Selected from group 31 to group 60:

Wherein R₅And R₆Separately selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl or its halogen substiuted Derivant, and

X^-For A can be made₂Form the anion of neutral group,

Work as A₂When group 55, n >=4 in formula (1).

In certain embodiments, A is worked as₂When group 55, in formula (1), n is not 3.

In certain embodiments, the structure of described compound is selected from:

And

Wherein, n is the integer of 1 to 50,

R₃Selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl or the derivant of its halogen substiuted, and

R₅Selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl or the derivant of its halogen substiuted.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes In compound, D and D₁Separately selected from group 7, group 10, group 15, group 16 or group 20, wherein R₃Selected from H, C₁-C₃₀ Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or the derivant of its halogen substiuted.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes In compound, A and A₁Separately selected from group 21 or group 23, wherein R₄Selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀ Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or the derivant of its halogen substiuted.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes In compound, A₂Selected from group 31, group 35, group 36, group 40, group 43, group 44, group 47 or group 55, wherein R₅With R₆Separately selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl or the derivant of its halogen substiuted.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes In compound, D and D₁Separately selected from group 7, group 10, group 15, group 16 or group 20, A and A₁Separately select From group 21 or group 23, and A₂Selected from group 31, group 35, group 36, group 40, group 43, group 44, group 47 or Group 55, wherein R₃Selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C3₀Carboxylic acid ester groups or its halogen take The derivant in generation, R₄Selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or its halogen substiuted Derivant and R₅And R₆Separately selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl or its halogen substiuted Derivant.

In certain embodiments, described formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes In compound, n is the integer of 1 to 30.In certain embodiments, described formula (1) to formula (6) containing receptor end group give being subject to In build oligo-thiophenes compound, n is the integer of 1 to 10.

In certain embodiments, described formula (1) to formula (6) to X in receptor type oligo-thiophenes compound^-It is selected from Halide ion, BF₄ ^-、PF₆ ^-、SO₃ ^-Or CF₃SO₃ ^-。

In certain embodiments, described formula (1) being selected to receptor type oligo-thiophenes compound to formula (6):

And

On the other hand, the application relate to preparing formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes The method of compound, wherein, the oligo-thiophenes containing receptor end group of the donor bridging oligo-thiophenes by dialdehyde base donor bridging With receptor end monomers, in the presence of solvent and catalyst, carry out Ke Neifeinageer (Knoevenagel) condensation reaction, Obtain describedization inclusion.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The solvent used in the method for fen compound is polar solvent.In certain embodiments, described formula (1) of preparing is to formula (6) solvent used in the method to receptor type oligo-thiophenes compound containing receptor end group is chloroform.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The catalyst used in the method for fen compound is alkali compounds.

The exemplary alkali compounds that can be used in the application includes but not limited to sodium carbonate, sodium hydride, potassium carbonate, uncle Butyl potassium alcoholate, triethylamine, N, N-lutidines, sodium hydride and ethyl diisopropyl amine.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The catalyst used in the method for fen compound is alkylamine.

The exemplary alkylamine that can be used in the application includes but not limited to triethylamine, N, N-lutidines and ethyl Diisopropylamine.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The catalyst used in the method for fen compound is triethylamine.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The consumption using catalyst in the method for fen compound is 0.1-20mol%.

In certain embodiments, described prepare formula (1) to formula (6) containing receptor end group to receptor type oligomerization thiophene The method of fen compound is carried out under a shielding gas.In certain embodiments, described formula (1) containing to formula (6) is prepared The method to receptor type oligo-thiophenes compound of receptor end group is carried out under argon shield.

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (1) is prepared Method is as follows,

Wherein, step is the most anhydrous, anaerobic, under argon shield, and Ni (dppp) Cl₂Catalyst, bromo-with 2-3 (and/or 4) alkane The Grignard reagent of base thiophene refluxes 1-7 days in ether；

2. step first carries out bromination, the oligomerization of donor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Ni (dppp) Cl₂Catalyst, Catalyst amount 0.1-20mol%, the Grignard reagent of bromo-with 2-3 (and/or 4) alkylthrophene refluxes 1-7 days in ether；

3. step first carries out bromination, the oligomerization of donor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Ni (dppp) Cl₂Catalyst, Catalyst amount 0.1-20mol%, the Grignard reagent of bromo-with 2-3 (and/or 4) alkylthrophene refluxes 1-7 days in ether；

Step is the most first by POCl₃Issue at ice bath with DMF and should make vilsmeier reagent, be added dropwise to oligo-thiophenes 1, in 2-dichloroethanes, Vilsmeier reagent excess, be heated to reflux 1-7 days；And

Step 5. room temperature, under argon shield, chloroform is solvent, and triethylamine is catalyst, catalyst amount 0.1- 20mol%, receptor end monomers A* excess, reacts 1-7 days.

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (2) is prepared Method is as follows,

Wherein, step is the most anhydrous, anaerobic, under argon shield, and Pd (PPh₃)₄For catalyst, catalyst amount 0.1- 20mol%, with 2-(tin trimethyl)-3-alkylthrophene in reflux in toluene 1-7 days；

2. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh₃)₄For catalyst, urge Agent consumption 0.1-20moi%, with 2-(tin trimethyl)-3-alkylthrophene in reflux in toluene 1-7 days；

4. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh₃)₄For catalyst, urge Agent consumption 0.1-20mol%, with 2-(tin trimethyl)-3-alkylthrophene in reflux in toluene 1-7 days；

Step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to receptor bridging Oligo-thiophenes 1, in 2-dichloroethanes, Vilsmeier reagent excess, be heated to reflux 1-7 days；And

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (3) is prepared Method is as follows,

In formula, D and D₁Can be the same or different,

Wherein, step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to donor The 1 of the oligo-thiophenes of bridging, in 2--dichloroethanes, oligo-thiophenes is 1: 0.5 with the amount ratio of the material of Vilsmeier reagent, adds Hot reflux 1-7 days；

Step 2. volume ratio be 1: 1 chloroform and glacial acetic acid in carry out bromination, the oligo-thiophenes of donor bridging with NBS It is 1: 1 with the amount ratio of the material of NBS；

Step is the most anhydrous, anaerobic, and under argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1- 20mol%, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double stannum monomers of D, heating reflux reaction 1-7 days；

Under step 4. argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1-20mol%, add Enter the K of appropriate 2moL/L₂CO₃Aqueous solution, bromo-derivative is 1: 0,5 with the ratio of the amount of the material of double pinacol borates of D, heating Back flow reaction 1-7 days；And

Step 5. room temperature, under argon shield, chloroform is solvent, and triethylamine is catalyst, catalyst amount 0.1- 20mol%, receptor end monomers excess, react 1-7 days.

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (4) is prepared Method is as follows,

Wherein, step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to receptor The 1 of the oligo-thiophenes of bridging, in 2-dichloroethane solution, the material of the oligo-thiophenes of receptor bridging and Vilsmeier reagent Amount ratio is 1: 0.5, is heated to reflux 1-7 days；

Step 2. volume ratio be 1: 1 chloroform and glacial acetic acid in carry out bromination, the oligo-thiophenes of receptor bridging with NBS It is 1: 1 with the amount ratio of the material of NBS；

Step is the most anhydrous, anaerobic, and under argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1- 20moi%, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double stannum monomers of D, heating reflux reaction 1-7 days；

Under step 4. argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1-20mol%, add Enter the K of appropriate 2mol/L₂CO₃Aqueous solution, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double pinacol borates of D, heating Back flow reaction 1-7 days；And

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (5) is prepared Method is as follows,

Wherein, under step 1. argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1- 20mol%, adds the K of appropriate 2mol/L₂CO₃The amount of the material of double pinacol borate monomers of aqueous solution, bromo-derivative and A Ratio is 1: 0.5, heating reflux reaction 1-7 days；And

Step 2. room temperature, under argon shield, chloroform is solvent, and triethylamine is catalyst, catalyst amount 0.1- 20mol%, receptor end monomers excess, react 1-7 days.

In certain embodiments, the side to receptor type oligo-thiophenes compound containing receptor end group of formula (6) is prepared Method is as follows,

In formula, A and A₁Can be the same or different.

In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6) The catalyst used in method is acidic catalyst.In certain embodiments, described prepare formula (1) to formula (6) give be subject to The catalyst used in the method for build oligo-thiophenes compound is acidulous catalyst.

Can be used in herein described formula (1) of preparing to the method to receptor type oligo-thiophenes compound of formula (6) In the example of exemplary acidulous catalyst include but not limited to ammonium acetate, propanoic acid ammonium and butanoic acid ammonium.

In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6) The catalyst used in method is ammonium acetate.

In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6) The solvent used in method is acid solution.In certain embodiments, described prepare formula (1) to formula (6) to receptor type The solvent used in the method for oligo-thiophenes compound is weakly acidic solution.

Can be used in herein described formula (1) of preparing to the method to receptor type oligo-thiophenes compound of formula (6) In the example of exemplary weakly acidic solution include but not limited to acetic acid, propanoic acid and butanoic acid.

In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6) The solvent used in method is acetic acid.

In certain embodiments, described formula (1) of preparing is to the side to receptor type oligo-thiophenes compound of formula (6) The consumption of catalyst described in method is excess.In certain embodiments, described prepare formula (1) to formula (6) to receptor Described in the method for type oligo-thiophenes compound, the consumption of catalyst is 10-30mol%.In certain embodiments, described system Described in the standby formula (1) method to receptor type oligo-thiophenes compound to formula (6), the consumption of catalyst is 20mol%.

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (1) is as follows,

Step is the most anhydrous, anaerobic, under argon shield, and Ni (dppp) Cl₂Catalyst, bromo-with 2-3 (and/or 4) alkylthrophene Grignard reagent reflux 1-7 days in ether；

Step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to donor bridging Oligo-thiophenes 1, in 2-dichloroethanes, Vilsmeier reagent excess, be heated to reflux 1-7 days；And

Step 5. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess, It is heated to reflux 24 hours.

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (2) is as follows,

Step is the most anhydrous, anaerobic, under argon shield, and Pd (PPh₃)₄For catalyst, catalyst amount 0.1-20mol%, with 2-(tin trimethyl)-3 (and/or 4)-alkyl thiophene is in reflux in toluene 1-7 days；

2. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh₃)₄For catalyst, urge Agent consumption 0.1-20mol%, with 2-(tin trimethyl)-3 (and/or 4)-alkylthrophene or 2-(tributyl tin)-3 (and/or 4) Alkylthrophene is in reflux in toluene 1-7 days；

3. step first carries out bromination, the oligomerization of receptor bridging with NBS in the chloroform that volume ratio is 1: 1 and glacial acetic acid Thiophene is 1: 2 with the amount ratio of the material of NBS, products therefrom anhydrous, anaerobic, under argon shield, Pd (PPh₃)₄For catalyst, urge Agent consumption 0.1-20mol%, with 2-(tin trimethyl)-3 (and/or 4)-alkylthrophene or 2-(tributyl tin)-3 (and/or 4) Alkylthrophene is in reflux in toluene 1-7 days；

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (3) is as follows,

In formula, D and D₁Can be the same or different,

Step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to donor bridging Oligo-thiophenes 1, in 2-dichloroethanes, oligo-thiophenes is 1: 0.5 with the amount ratio of the material of Vilsmeier reagent, heats back Flow 1-7 days；

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (4) is as follows,

Step is the most first by POCl₃Issue at ice bath with DMF and should make Vilsmeier reagent, be added dropwise to receptor bridging Oligo-thiophenes 1, in 2-dichloroethanes, the oligo-thiophenes of receptor bridging is 1 with the amount ratio of the material of Vilsmeier reagent: 0.5, it is heated to reflux 1-7 days；

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (5) is as follows,

Under step 1. argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1-20mol%, add Enter the K of appropriate 2mol/L₂CO₃Aqueous solution, bromo-derivative and A₁The ratio of amount of material of double pinacol borate monomers be 1: 0.5, Heating reflux reaction 1-7 days；And

Step 2. acetic acid is solvent, and ammonium acetate is catalyst, catalyst amount 20mol%, receptor end monomers A* excess, It is heated to reflux 24 hours.

In certain embodiments, the method to receptor type oligo-thiophenes compound preparing formula (6) is as follows,

In formula, A and A₁Can be the same or different,

Under step 1. argon shield, toluene is solvent, Pd (PPh₃)₄For catalyst, catalyst amount 0.1-20mol%, add Enter the K of appropriate 2mol/L₂CO₃Aqueous solution, bromo-derivative is 1: 0.5 with the ratio of the amount of the material of double pinacol borate monomers of A, Heating reflux reaction 1-7 days；And

In certain embodiments, formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes compound May be used for preparing photovoltaic device is solar cell device.

In certain embodiments, formula (1) to formula (6) containing receptor end group to receptor type oligo-thiophenes compound May be used for preparing photovoltaic device is the photoactive layer in solar cell device.

Another further aspect, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound The triode device of active layer.

Another aspect, the application relate to comprising have formula (1) to formula (6) to receptor type oligo-thiophenes compound The photovoltaic device of active layer.

In certain embodiments, solar cell device comprise have formula (1) to formula (6) to receptor type oligomerization The photoactive layer of thiophene compound.

Other aspects, the application relates to selected from following compound:

The application containing receptor end group in receptor type oligo-thiophenes photoelectric material, owing to oligo-thiophenes is owing to having Higher hole mobility, so the application's also has higher hole mobility to receptor type oligo-thiophenes photoelectric material.

The combining polymer to receptor type oligo-thiophenes photoelectric material and being commonly conjugated little containing receptor end group of the application The advantage of molecule, has the advantages such as accurate molecular weight, structure-controllable, easy purification with common polymer phase ratio, is total to common Yoke small molecular phase has preferable dissolubility than again, can be made into thin film, beneficially field-effect transistor and include solaode Device is in the preparation of interior photovoltaic device.

The application relate to containing organic small molecule dyes receptor end group in receptor type oligo-thiophenes compound, due to Oligo-thiophenes has higher hole mobility, and organic molecule dyestuff has high electron-withdrawing and molar absorption coefficient, So this class involved by the application also has higher hole mobility and mole suction to receptor type oligo-thiophenes compound Backscatter extinction logarithmic ratio.

What the application related to combines poly-containing organic small molecule dyes receptor end group to receptor type oligo-thiophenes compound Compound and be conjugated the advantage of little molecule, has accurate molecular weight, controlled structure, the purest with conventional polymer phase ratio Change process, has preferable dissolubility with common conjugation small molecular phase than again, makes solvation process be possibly realized, can be made into thin Film, is conducive to preparing high performance organic field effect tube and the photovoltaic device including organic solar cell device.

Use the preparing to receptor type oligo-thiophenes compound containing organic small molecule dyes receptor end group that the application relates to Organic thin film solar cell there is the feature of dye-sensitized cell material height molar absorption coefficient, withed a hook at the end organic simultaneously Solaode can become the feature of fexible film.

Hereinafter, the present invention is explained in detail by below embodiment with reference to the accompanying drawings to be more fully understood that the present invention Various aspects and advantage.It will be appreciated, however, that below example is nonrestrictive being simply used for, and the present invention is described Some embodiment.

Embodiment

Embodiment 1

The synthesis of oligo-thiophenes precursor

1) synthesis of 2-bromo-3-octyl thiophene

60mL DMF is added in the 250mL bottle with two necks filling 3-octyl thiophene (10.00g, 50.93mmol).Cryosel is bathed Under, instill the 60mL DMF solution of NBS (9.26g, 52.03mmol).Drip and finish, be slowly raised to room temperature, stirred overnight at room temperature.Stop Reaction, pours in 200mL water, and dichloromethane (60mL × 4) extracts.Organic facies successively with potassium hydroxide aqueous solution (2M, 100mL), saturated aqueous common salt (100mL) and water (100mL × 2) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether For eluent, crossing post and separate, obtain 12.60g oily liquids, productivity is 89%.

Its structural formula is as follows:

2) 3,3 "-dioctyl-2,2 ': 5 ', the 2 " synthesis of-three thiophene (3T)

20mL ether is added in the 100mL bottle with two necks filling magnesium chips (704mg, 28.96mmol), under argon shield, slow Slow instillation 2-bromo-3-octyl thiophene (4.00g, 14.56mmol), glycol dibromide (1.37g, 7.28mmol) and 20mL ether Mixed liquor.Drip and finish, be heated to reflux 4 hours, drop to room temperature.Gained Grignard reagent is slowly dropped into and fills Ni (dppp) Cl₂ (177mg, 0.326mmol), 2,5-dibromo thiophene (1.40g, 5.56mmol) and the mixed liquor of 25mL ether.Drip and finish, heat back Flow 18 hours.Dropping to room temperature, add 20mL dilute hydrochloric acid (2M), pour in 200mL water, dichloromethane (100mL × 3) extracts.Have Aqueous sodium carbonate (2M, 100mL) used the most successively by machine, and saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is done Dry.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 2.30g pale yellowish oil liquid, and productivity is 84%.

Its structural formula is as follows:

3) 5-tributyl tin-3,3 "-dioctyl-2,2 ': 5 ', the 2 " synthesis of-three thiophene (BS3T)

Under argon shield, in the 250mL there-necked flask filling three thiophene (3.65g, 7.72mmol), add 100mLTHF. It is cooled to-78 DEG C, after the hexane solution (3.3ml, 2.4M, 2.92mmol) of dropping n-BuLi, is warming up to-40 DEG C of reaction 1h. It is cooled to-78 DEG C again, instills tributyltin chloride (3.02g, 9.26mmol), stirred overnight at room temperature.Pour reactant into 100mL In water, ethyl acetate (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, obtains orange-yellow oily liquids 4.83g, productivity 82%.

Its structural formula is as follows:

4) 5,5 "-two bromo-3,3 "-dioctyl-2,2 ': 5 ', 2 "-three thiophene (3TBr₂) synthesis

In the 250mL bottle with two necks filling three thiophene 1 (1.20g, 2.54mmol), add 30mL chloroform and 30mL ice second Acid, is cooled at 0 DEG C, is dividedly in some parts by NBS (0.96g, 5.39mmol), and about 20min adds.After stirring 3 hours under room temperature, will Reactant is poured in 100mL water, and dichloromethane (100mL × 3) extracts.Organic facies successively with aqueous sodium carbonate (2M, 100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether be Eluent, crosses post and separates, obtain 1.60g yellow oily liquid, and productivity is 100%.

Its structural formula is as follows:

5) 3,3 ', 3 ' ", 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 ' ": 5 ' ", the 2 " " synthesis of-five thiophene (5T)

20mL ether, argon shield, room temperature is added in the 100mL bottle with two necks filling magnesium powder (0.36g, 14.48mmol) Lower instillation 2-bromo-3-octyl thiophene (2.00g, 7.28mmol), glycol dibromide (0.34g, 1.82mmol) and 20mL ether Mixed liquor, drip finish, be heated to reflux 4 hours.It is added dropwise to gained Grignard reagent under argon shield fill dibromo three thiophene 2 (1.54g, 2.44mmol), Ni (dppp) Cl₂In the mixed liquor of (90mg, 0.17mmol) and 20mL ether, about half an hour drips off. It is heated to reflux 20 hours, after dropping to room temperature, adds dilute hydrochloric acid (20mL, 1M), stir 5 minutes, reactant liquor is poured into 100mL water In, dichloromethane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 1.75g gold oil liquid Body, productivity is 83%.

Its structural formula is as follows:

6) 5,5 " "-two bromo-3,3 ', 3 ' ", 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 ' ": 5 ' ", 2 " "-five thiophene (5TBr₂) synthesis

In the 250mL bottle with two necks filling five thiophene 3 (1.15g, 1.33mmol), add 30mL chloroform and 30mL ice second Acid, is cooled at 0 DEG C, is dividedly in some parts by NBS (0.50g, 2.81mmol), and about 20min adds.After stirring 3 hours under room temperature, will Reactant is poured in 100mL water, and dichloromethane (100mL × 3) extracts.Organic facies successively with aqueous sodium carbonate (2M, 100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether be Eluent, crosses post and separates, obtain 1.22g yellow oily liquid, and productivity is 90%.

Its structural formula is as follows:

7) 3,3 ', 3 ", 3 ' ", 3 " ", 3 " " "-six octyl group-2,5 ': 2 ', 5 ": 2 ", 2 ' ": 5 ' ", 2 " ": 5 " ", 2 ' " ": 5 ' " ", 2 " " " synthesis of-seven thiophene (7T)

In the 100mL bottle with two necks filling magnesium powder (0.18g, 7.24mmol), add 15mL ether, instill 2-under room temperature bromo- 3-octyl thiophene (1.00g, 3.64mmol), glycol dibromide (0.17g, 0.91mmol) and the mixed liquor of 15mL ether, drip Finish, be heated to reflux 4 hours.Be added dropwise to gained Grignard reagent under argon shield to fill dibromo five thiophene 4 (1.24g, 1.22mmol), Ni (dppp) Cl₂In the mixed liquor of (59mg, 0.11mmol) and 20mL ether, about half an hour drips off.Heat back Flow 20 hours, after dropping to room temperature, add dilute hydrochloric acid (20mL, 1M), stir 5 minutes, reactant liquor is poured in 100mL water, dichloro Methane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous Sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, obtain 1.09g gold oil liquid, productivity It is 72%.

Its structural formula is as follows:

8) 5,5 "-dicarbaldehyde-3,3 "-dioctyl-2,2 ': 5 ', 2 "-three thiophene (3T (CHO)₂) synthesis

At 0 DEG C, by POCl₃(0.71mL, 7.74mmol) is slowly dropped in DMF (3.00mL, 38.70mmol), stirring 10 minutes, it is added dropwise to gained liquid under argon shield fill 3T (1.22g, 2.58mmol) and the mixing of 30mL1,2-dichloroethanes In mixed liquor.Being heated to 60 DEG C react 12 hours, be cooled to room temperature, pour in 200mL frozen water, sodium carbonate neutralizes, dichloromethane (100mL × 3) extract.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous slufuric acid Sodium is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluent, crosses post and separates, 1.13g coral solid, productivity is 83%.

Its structural formula is as follows:

9) 5,5 " "-dicarbaldehyde-3,3 ', 3 ' ", 3 " "-four octyl group-2,5 ': 2 ', 5 ": 2 ", 2 ' ": 5 ' ", 2 " "-five thiophene (5T(CHO)₂) synthesis

The same 3T of method (CHO)₂Synthesis.Obtaining dark orange solid, productivity is 85%.

Its structural formula is as follows:

10) 5,5 " " "-diformazan aldehyde radical-3,3 ', 3 ", 3 " ", 3 " ", 3 " " "-six octyl group-2,5 ': 2 ', 5 ": 2 ", 2 ' ": 5 ' ", 2 " ": 5 " ", 2 ' " ": 5 ' " ", 2 " " "-seven thiophene (7T (CHO)₂) synthesis

The same 3T of method (CHO)₂Synthesis.Obtaining 1.13g brown solid, productivity is 81%.

Its structural formula is as follows:

11) synthesis of compound TBT

In the bottle with two necks of 250mL, addition 4,7-dibromo diazosulfide (6.00g, 20.4mmol), 2-tributyl tin- 4-octyl thiophene (55g, 113.3mmol), and Pd (PPh₃)₂Cl₂(320mg, 0.46mmol).120mL is added under argon shield Anhydrous new steaming oxolane.It is heated to reflux 24 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3) Taking, organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates, Obtaining 8.8g red solid, productivity is 82%.

Its structural formula is as follows:

12) synthesis of compound BrTBTBr

In the bottle with two necks of 100mL, add compound TBT (0.96g, 1.83mmol), 60mL chloroform.Under cryosel bath in batches Add NBS (0.65g, 3.66mmol).Keep time thermotonus 1 hour, remove ice bath.Room temperature reaction is overnight.Pour 100mL water into In, extracting with dichloromethane (100mL × 3), organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, Crossing post with petroleum ether for eluant to separate, obtain 1.08g red solid, productivity is 86%.

Its structural formula is as follows:

13) synthesis of compound 2TB2T

In the bottle with two necks of 100mL, add compound BrTBTBr (1.02g, 1.49mmol), 2-tributyl tin-4-octyl group Thiophene (2.18g, 4.48mmol), and Pd (PPh₃)₂Cl₂(105mg, 0.15mmol).65mL is added anhydrous newly under argon shield Steam oxolane.It is heated to reflux 40 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3), have Machine is washed with water (100mL) mutually, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates, 1.26g violet solid, productivity is 94%.

Its structural formula is as follows:

14) synthesis of compound Br2TB2TBr

In the bottle with two necks of 100mL, add compound 2TB2T (0.86g, 0.94mmol), 70mL chloroform.Cryosel bathes lower point Criticize and add NBS (0.29g, 1.61mmol).Keep time thermotonus 1 hour, remove ice bath.Room temperature reaction is overnight.Pour 100mL into In water, extracting with dichloromethane (100mL × 3), organic phase washed with water (100mL) is washed, and anhydrous sodium sulfate is dried.Decompression removes molten Agent, crosses post with petroleum ether for eluant and separates, obtain 0.79g red solid, and productivity is 46%.

Its structural formula is as follows:

15) synthesis of compound 3TB3T

In the bottle with two necks of 250mL, add compound Br2TB2TBr (130mg, 0.12mmol), 3-butyl tin-4-octyl group Thiophene (357mg, 0.36mmol), and Pd (PPh₃)₂Cl₂(8.5mg,0.01mmol).60mL is added anhydrous newly under argon shield Steam oxolane.It is heated to reflux 40 hours, stopped reaction.Pour in 100mL water, extract with dichloromethane (100mL × 3), have Machine is washed with water (100mL) mutually, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, crosses post with petroleum ether for eluant and separates, 139mg black solid, productivity is 89%.

Its structural formula is as follows:

16) synthesis of 5TCHO

At 0 DEG C, by POCl₃(0.84mL, 9.2mmol) is slowly dropped in DMF (4.24mL, 55.0mmol), stirs 10 Minute, take the gained liquid of 1/10th under argon shield and be added dropwise to fill 5T (0.79g, 0.92mmol) and 30mL1,2-bis-chloroethene In the mixed liquor of alkane.Being heated to 70 DEG C react 24 hours, be cooled to room temperature, pour in 200mL frozen water, sodium carbonate neutralizes, dichloromethane Alkane (100mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous sulfur Acid sodium is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluent, crosses post and separates, Obtaining 0.46g red solid, productivity is 56%.

Its structural formula is as follows:

17) synthesis of Br5TCHO

In the 100mL bottle with two necks filling 5TCHO (0.32g, 0.36mmol), add 30mL chloroform and 30mL glacial acetic acid, Being dividedly in some parts by NBS (64mg, 0.36mmol), about 20min adds.After stirring 3 hours under room temperature, pour reactant into 100mL In water, dichloromethane (100mL × 3) extracts.Organic facies is successively with aqueous sodium carbonate (2M, 100mL), saturated aqueous common salt (100mL) washing with water (100mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether as eluent, crosses post and separates, 0.31g red solid, productivity is 89%.

Its structural formula is as follows:

18) synthesis of compound 3TB3T (CHO)

Method is with the synthesis of 5TCHO.Obtaining 1.08g brown solid, productivity is 70%.

Its structural formula is as follows:

19) synthesis of compound Br3TB3T (CHO)

Method is with the synthesis of Br5TCHO.Obtaining 0.82g brown solid, productivity is 81%.

Its structural formula is as follows:

20) synthesis of compound D3TBT

Under argon shield, fill to dibromo bithiophene (0.40g, 1.34mmol), single tributyl tin three thiophene (2.46g, The bottle with two necks of 40mL dry toluene 3.23mmol) and adds triphenylphosphine palladium (0.078g, 0.068mmol) 110 DEG C refluxed Night.Being poured into by reactant liquor in 100mL water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (50mL), saturated common salt Water (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, mistake Post separates, and obtains 0.60g Orange red solid, and productivity is 41%.

Its structural formula is as follows:

21) compound 3T (TT) 3T (CHO)₂Synthesis

At 0 DEG C, by POCl₃(0.76mL, 8.32mmol) is slowly dropped in DMF (3.19mL, 41.25mmol), stirring 10 minutes, gained liquid is added dropwise under argon shield to fill D3TBT (0.60g, 0.55mmol) and 25mL1,2-dichloroethanes In mixing mixed liquor.Being heated to 60 DEG C react 12 hours, be cooled to room temperature, pour in 100mL frozen water, sodium carbonate neutralizes, dichloromethane Alkane (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous slufuric acid Sodium is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluant, crosses post and separates, 0.40g black solid, productivity is 63%.

Its structural formula is as follows:

Embodiment 2

Under argon shield, filling dialdehyde base three thiophene 3T (CHO)₂(200mg, 0.38mmol) and 50mL chloroform 100mL bottle with two necks adds three triethylamines and 0.1mL cyan-acetic ester, under argon shield, is stirred at reflux overnight.Drop to room Temperature, pours in 200mL water, stands, sucking filtration, solid washing with alcohol, by gained solid with dichloromethane as eluent, crosses post and divides From, obtaining 226mg brown solid, productivity is 83%.¹H NMR (400MHz, CHCl₃): δ 8.23 (s, 2H), 7.61 (s, 2H), 7.33 (s, 2H), 4.34-4.40 (q, J=7.0,4H), 2.83 (t, J=7.5Hz, 4H), 1.69 (m, 4H), 1.40 (t, J=7.0Hz, 6H), 1.27 (m, 20H), 0.87 (t, J=6.1Hz, 6H) .HRMS (MALDI-FTICR): C₄₀H₅₀N₂O₄S₃[M]⁺, theoretical value, 718.2933；Measured value, 718.2937.

Its structural formula is as follows:

Embodiment 3

Method is with embodiment 2.Obtaining dark green solid, productivity is 80%.¹H NMR (400MHz, CHCl₃): δ 8.15 (s, 2H), 7.49 (s, 2H), 7.13 (s, 2H), 7.09 (s, 2H), 4.29 (q, J=6.6Hz, 4H), 2.74 (t, J=6.6Hz, 8H), 1.61 (m, 8H), 1.32 (t, J=6.5Hz, 6H), 1,21 (m, 40H), 0.80 (t, J=6.1Hz, 12H) .HRMS (MALDI- FTICR): C₆₄H₈₆N₂O₄S₅[M]⁺, theoretical value, 1106.5191；Measured value, 1106.5188,

Its structural formula is as follows:

Embodiment 4

Method is with embodiment 2.Obtaining 180mg dark green solid, productivity is 75%.¹HNMR(400MHz,CHCl₃): δ 8.14 (s, 2H), 7.49 (s, 2H), 7.12 (s, 2H), 7.05 (s, 2H), 6.96 (s, 2H), 4.27-4.31 (q, J=7.1Hz, 4H), 2.75 (t, J=7.8Hz, 12H), 1.58-1.68 (m, 12H), 1.32 (t, J=7.1Hz, 6H), 1.21 (m, 60H), 0.80 (t, J= 6.1Hz, 18H) .HRMS (MALDI-FTICR): C₈₈H₁₂₂N₂O₄S₇[M]⁺, theoretical value, 1494.7450；Measured value, 1494.7460。

Its structural formula is as follows:

Embodiment 5

Method is with embodiment 2.Replacing cyan-acetic ester with cyanoacetic acid monooctyl ester, productivity is 81%.¹H NMR (400MHz, CHCl₃): δ 8.20 (s, 2H), 7.56 (s, 2H), 7.19 (s, 2H), 7.12 (s, 2H), 7.03 (s, 2H), 4.29 (t, J=6.7Hz, 4H), 2.83m, 12H), 1.71 (m, 16H), 1.42-1.29 (m, 80H), 0.88 (t, J=5.9Hz, 24H) .MALDI-TOF MS (m/z): C₁₀₀H₁₄₆N₂O₄S₇[M]⁺, theoretical value, 1662.93；Measured value, 1662.93.

Its structural formula is as follows:

Embodiment 6

Method is with embodiment 2.Replacing cyan-acetic ester with cyanoacetic acid-2-Octyl Nitrite, productivity is 78%.¹HNMR (400MHz,CHCl₃): δ 8.20 (s, 2H), 7.57 (s, 2H), 7.19 (s, 2H), 7.12 (s, 2H), 7.03 (s, 2H), 4.22 (d, J=Hz, 4H), 2.83 (m, 12H), 1.71 (m, 14H), 1.42 (m, 16H), 1.31 (m, 60H), 0.94 (t, J=8.1Hz, 12H), 0.88 (t, J=5.9Hz, 18H) .MALDI-TOF MS (m/z): C₁₀₀H₁₄₆N₂O₄S₇[M]⁺, theoretical value, 1662.93；Real Measured value, 1662.93.

Its structural formula is as follows:

Embodiment 7

9 (0.16g, 0.12mmol), 40mL chloroform is added in the bottle with two necks of 100mL.0.1mL tri-is added under argon shield Ethamine, instills 0.4mL Cyanoacetyl-Cyacetazid, and room temperature reaction is overnight.Pour in 100mL water, extract with dichloromethane (100mL × 3), organic Washing with water (100mL) mutually, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume of petroleum ether and dichloromethane Ratio 1: 1) it is that eluant crosses post separation, obtain 0.13g black solid, productivity is 76%.¹H NMR (400MHz, CHCl₃): δ 8.40 (s, 2H), 7.98 (s, 2H), 7.84 (s, 2H), 7.11 (d, J=7.7Hz, 2H), 7.07 (br, 2H), 4.37 (q, J=7.0Hz, 4H), 2.83 (m, 12H), 1.71 (m, 12H), 1.40 (t, J=7.0Hz, 6H), 1.29 (m, 60H), 0.89 (br, 18H) .MS (MALDI-TOF): calcd for C₈₆H₁₁₂N₆S₇[M]⁺, 1452.70；Foud, 1452.67.

Its structural formula is as follows:

Embodiment 8

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0.26g, 0.20mmol), 1,3-diethyl-2-sulfur It is dried in chloroform bottle with two necks three triethylamines of instillation for barbiturates (0.20g, 1.00mmol) and 50mL, was stirred at room temperature Night.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) Washing with water (50mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane as eluant, crosses post and separates, obtain 0.23g black solid, productivity is 70%.MALDI-TOF MS (m/z): C₉₅H₁₃₄N₄O₄S₈[M]⁺, theoretical value, 1650.82；Actual measurement Value, 1650.83.

Its structural formula is as follows:

Embodiment 9

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0.26g, 0.20mmol), diethyl malonate (0.16g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three triethylamines of instillation, stirred overnight at room temperature.Pour into In 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane as eluant, crosses post and separates, obtain 0.24g Dark red solid, productivity is 75%.MALDI-TOF MS (m/z): C₉₂H₁₃₂O₈S₇[M]⁺, theoretical value, 1588.80；Measured value, 1588.81。

Its structural formula is as follows:

Implement fall 10

1)(3TB3T)T(3TB3T)(CHO)₂Synthesis

Addition 50mL toluene in the bottle with two necks of 100mL, Br3TB3T (CHO) (0.28g, 0.20mmol), 2,5-bis-(three Methyl stannum) thiophene (41mg, 0.10mmol).Pd (PPh is added under argon shield₃)₄(20mg, 0.017mmol), is heated to 90 DEG C Backflow.After 24 hours, being poured into by reactant in 100mL water, dichloromethane (100mL × 3) extracts.Organic facies uses saturated food successively Saline (100mL) and water (100mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, mixed with petroleum ether and dichloromethane Closing liquid (volume ratio 1: 1) is that eluent crosses post separation, obtains 0.21g black solid, and productivity is 72%.

2) synthesis of target compound

Under argon shield, filling (3TB3T) T (3TB3T) (CHO)₂(0.22g, 0.08mmol), cyan-acetic ester (0.3mL) it is dried in the 100mL bottle with two necks of chloroform instills three triethylamines, stirred overnight at room temperature with 60mL.Pour 100mL into In water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) are washed Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane and petroleum ether (volume ratio is for 1: 1) as eluent, crosses post and divides From, obtaining 0.19g black solid, productivity is 82%.MS (MALDI-TOF): C₁₇₂H₂₃₄N₆O₄S₁₅[M]⁺, theoretical value, 2927.41； Measured value, 2927.43.

Its structural formula is as follows:

Embodiment 11

1)11T(CHO)₂Synthesis

50mL toluene, Br5TCHO (0.39g, 0.40mmol), 2,5-mono-(trimethyls are added in the bottle with two necks of 100mL Stannum) thiophene (0.08g, 0.20mmol).Pd (PPh is added under argon shield₃)₄(20mg, 0.017mmol), is heated to 90 DEG C and returns Stream.After 24 hours, being poured into by reactant in 100mL water, dichloromethane (100mL × 3) extracts.Organic facies uses saturated common salt successively Water (100mL) and water (100mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether and the mixing of dichloromethane Liquid (volume ratio 1: 1) is that eluent crosses post separation, obtains 0.30g brown solid, and productivity is 81%.

2) synthesis of target compound

Under argon shield, filling dialdehyde base oligo-thiophenes 11T (CHO)₂(0.28g, 0.15mmol), cyan-acetic ester (0.3mL) it is dried in the 100mL bottle with two necks of chloroform instills three triethylamines, stirred overnight at room temperature with 60mL.Pour 100mL into In water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) are washed Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane and petroleum ether (volume ratio is for 1: 1) as eluent, crosses post and divides From, obtaining 0.26g black solid, productivity is 84%.MS (MALDI-TOF): C₁₂₀H₁₆₂N₂O₄S₁₁[M]⁺, theoretical value, 2046.95； Measured value, 2046.97.

Its structural formula is as follows:

Embodiment 12

1)5T(BDT)5T(CHO)₂Synthesis

60mL toluene, Br5TCHO (194g, 0.20mmol), 2,6-bis-(trimethyls are added in the bottle with two necks of 100mL Stannum)-4,8-two (2-second hexyl) benzene 1,4-Dithiapentalene (0.08g, 0.10mmol).Pd (PPh is added under argon shield₃)₄(20mg, 0.017mmol), 90 DEG C of backflows it are heated to.After 24 hours, being poured into by reactant in 100mL water, dichloromethane (100mL × 3) extracts Take.Organic facies is washed with saturated aqueous common salt (100mL) and water (100mL) successively, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, It is that eluent is crossed post and separated with petroleum ether and the mixed liquor (volume ratio 1: 1) of dichloromethane, obtains 0.16g red brown solid, produce Rate is 73%.

2) synthesis of target compound

Under argon shield, filling dialdehyde base oligo-thiophenes 5T (BDT) 5T (CHO)₂(0.11g, 0.05mmol), cyano group second Misery ester (0.2mL) and 40mL are dried in the 100mL bottle with two necks of chloroform three triethylamines of instillation, stirred overnight at room temperature.Fall Entering in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane and petroleum ether (volume ratio is for 2: 1) as drip washing Agent, crosses post and separates, obtain 0.10g black solid, and productivity is 77%.¹H NMR (400MHz, CHCl₃): δ 8.20 (s, 2H), 7.56 (s, 2H), 7.26 (s, 2H), 7.20 (s, 2H), 7.14 (br, 8H), 4.28 (t, J=6.5Hz, 4H3,4.20 (br, 4H), 2.82 (br, 16H), 1.86 (s, 2H), 1.71 (m, 24H), 1.29 (m, 112H), 1.07 (t, J=7.0Hz, 6H), 1.00 (br, 6H), 0.89 (br, 30H) .MS (MALDI-TOF): [M]⁺, theoretical value, 2577.36；Measured value, 2577.82.

Its structural formula is as follows:

Embodiment 13

1)5TB5T(CHO)₂Synthesis

In the bottle with two necks of 100mL, add 50mL toluene, deaerate 10 minutes.Add Br5TCHO (0.29g, 0.30mmol), 4,7-double (4,4,5,5-tetramethyl-1,3,2-dioxy borines) diazosulfides (58mg, 0.15mmol), the K of 2M₂CO₃Aqueous solution 8mL.Pd (PPh is added under argon shield₃)₄(20mg, 0.017mmol), is heated to 90 DEG C of backflows.After 24 hours, reactant is fallen Entering in 100mL water, dichloromethane (100mL × 3) extracts.Organic facies is washed with saturated aqueous common salt (100mL) and water (100mL) successively Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with the mixed liquor (volume ratio 1: 1) of petroleum ether and dichloromethane as eluent Crossing post to separate, obtain 0.21g dark red solid, productivity is 72%.

2) synthesis of target compound

Under argon shield, filling 5TB5T (CHO) 2 (0.38g, 0.20mmol), cyan-acetic ester (0.3mL) and 60mL is dried in the 100mL bottle with two necks of chloroform three triethylamines of instillation, stirred overnight at room temperature.Pour in 100mL water, dichloro Methane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) washing, anhydrous sulfur Acid sodium is dried.Removal of solvent under reduced pressure, with dichloromethane as eluent, crosses post and separates, obtain 0.37g black solid, and productivity is 88%.¹H NMR (400MHz, CHC13): δ 8.18 (s, 2H), 7.94 (d, J=Hz, 2H), 7.75 (d, J=Hz, 2H), 7.52 (s, 2H), 7.17 (s, 2H), 7.09 (m, 6H), 7.92-7.97 (m, 1H), 4.34 (q, J=Hz, 4H), 2.80 (br, 16H), 1.70 (m, 16H), 1.29 (m, 86H), 0.89 (m, 24H).MS (MALDI-TOF): C₁₂₂H₁₆₂N₄O₄S₁₁[M]⁺, theoretical value, 2098.95； Measured value, 2099.02.

Its structural formula is as follows:

Embodiment 14

Dialdehyde base seven thiophene 7T (CHO) is added in 50mL single port bottle₂(50mg, 0.038mmol) and 30mL acetic acid, stirring Make to be uniformly dispersed, add 3-ethyl Lip river tannin (20mg, 0.12mmol) and ammonium acetate (20mg, 0.12mmol), agitating heating Backflow is overnight.Dropping to room temperature, pour in 200mL water, add the extraction of 50mL dichloromethane, organic facies adds 50mL washing (three Secondary).Organic facies anhydrous magnesium sulfate is dried, and filters, is spin-dried for, and with dichloromethane and petroleum ether (1: 1) as eluent, column chromatography is divided From, obtaining 60mg brown solid, productivity is 98.4%.¹HNMR (400MHz, CHC13): 67.764 (s, 2H) 7.209 (s, 2H), 7.100 (s, 4H), 7.011 (s, 2H), 4.21 (q, 4H, J=7.0Hz), 2.74 (t, 12H, J=6.7Hz), 1.709 (m, 12H), 1.300 (m, 60H), 0.882 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C₈₈H₁₂₂N₂O₂S₁₁[M]⁺, theoretical value: 1592.64；Measured value: 1591.10

Its structural formula is as follows:

Implement fall 15

Addition dialdehyde base seven thiophene (100mg, 0.077mmol) in 50mL single port bottle, hexafluoro acetylacetone,2,4-pentanedione (77mg, 0.37mmol), 20mL acetic acid, 5mL chloroform, stirring and dissolving are added.Under agitation heated overnight at reflux.Drop to room temperature, pour into In 200mL water, adding the extraction of 50mL dichloromethane, organic facies adds 50mL washing (once), 50ml saturated sodium bicarbonate solution Washing (once), 50mL washes (once).Organic facies anhydrous magnesium sulfate is dried, and filters, is spin-dried for, with dichloromethane and petroleum ether (2: 1) it is eluent, pillar layer separation, obtain 120mg dark green solid, productivity is 93.0%.¹H NMR (400MHz, CHC13): δ 7.878 (s, 2H) 7.396 (s, 2H), 7.155 (8,4H), 6.976 (s, 2H), 2.757 (t, 12H, J=6.7Hz), 1.630 (m, 12H), 1.215 (m, 60H), 0.810 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C₈₈H₁₁₂F₁₂O₄S₇[M]⁺, theoretical Value: 1686.26；Measured value: 1685.32

Its structural formula is as follows:

Embodiment 16

Addition dialdehyde base seven thiophene (50mg, 0.038mmol) in 25mL bottle with two necks, n-butylamine (44mg, 0.6mmol), add 10mL dichloromethane stirring and dissolving, add anhydrous sodium sulfate (1g, 7ml), be stirred at room temperature 24 hours.Will Reaction system is spin-dried for, and adds 15mL benzene and dissolves, adds trifluoroacetic ethyl acetoacetate (73mg, 0.4mmol), acetic anhydride (0.1g, 0.98mmol), after being heated to reflux 4 hours, being down to room temperature, be spin-dried for solvent, add 50mL dichloromethane and again dissolve, 50mL washes (three times), organic facies anhydrous magnesium sulfate is dried, pillar layer separation, obtains dark green solid 32mg, productivity 52.6%.¹H NMR (400MHz, CHC13): δ 7.853 (s, 2H) 7.409 (s, 1H), 7.342 (s, 1H) 7.134 (s, 4H), 7.021 (s, 2H), 4.32 (dd, 4H, J=6.9Hz, J=32.3Hz) 2.803 (t, 12H, J=6.7Hz), 1.685 (m, 18H), 1.259 (m, 60H), 0.878 (t, 18H, J=6.6Hz) .HRMS (MALDI-FTICR): C₉₀H₁₂₂F₆O₆S₇[M]⁺, theoretical value: 1638.37；Measured value: 1637.72

Its structural formula is as follows:

Embodiment 17

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0,13g, 0.10mmol), 1,3-dimethyl-Ba Bi Appropriate acid (0.156g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three piperidines of instillation, stirred overnight at room temperature.Pour into In 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-ethyl acetate as eluant, crosses post and separates, The black-and-blue solid of 0.12g, productivity is 79%.MALDI-TOF MS (m/z): C₉₀H₁₂₄N₄O₆S₇[M]⁺, theoretical value: 1580.76；Real Measured value: 1580.71

Its structural formula is as follows:

Implement fall 18

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0.13g, 0.10mmol), 2,2,2-trifluoroethyls 2-cyan-acetic ester (0.167g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three triethylamines of instillation, and room temperature is stirred Mix overnight.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) washing with water (50mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, crosses post Separating, obtain 0.11g dark green solid, productivity is 70%.MALDI-TOFMS (m/z): C₈₈H₁₁₆F₆N₂O₄s₇[M]⁺, theoretical value: 1603.69；Measured value: 1603.71

Its structural formula is as follows:

Embodiment 19

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0.13g, 0.10mmol), 2,2,3,3,3-five fluorine Propyl group 2-cyan-acetic ester (0.217g, 1.00mmol) and 50mL are dried in chloroform bottle with two necks three triethylamines of instillation, room Temperature is stirred overnight.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated common salt Water (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, mistake Post separates, and obtains 0.12g dark green solid, and productivity is 70%.MALDI-TOPMS (m/z): C₉₀H₁₁₆F₁₀N₂O₄S₇[M]⁺, theoretical value: 1702.68；Measured value: 1702.70

Its structural formula is as follows:

Embodiment 20

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO)₂(0.13g, 0.10mmol), 2,2,3,3,4,4,5, 5,6,6,7,7,8,8,8-15 fluorine octyl group 2-cyan-acetic ester (0.467g, 1.00mmol) and 50mL is dried chloroform twoport Three triethylamines, stirred overnight at room temperature is instilled in Ping.Pouring in 100mL water, dichloromethane (20mL × 3) extracts.Organic facies depends on Secondary water (50mL), saturated aqueous common salt (50mL) and water (50mL) are washed, and anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloro Methane-petroleum ether is eluant, crosses post and separates, obtains 0.16g dark green solid, productivity 73%.MALDI-TOF MS (m/z): C₁₀₀H₁₁₆F₃₀N₂O₄S₇[M]⁺, theoretical value: 2203.65；Measured value: 2203.71

Its structural formula is as follows:

Embodiment 21

Under argon shield, filling dialdehyde base seven thiophene 7T (CHO) 2 (0.13g, 0.10mmol), (E)-5-(3-ethyl- 5-carbonyl thiazoline 2-ylide)-3-octyl group-2,4-dicarbapentaborane thiazoline (0,356g, 1.00mmol), ammonium acetate (0.077g, In 1mmol) in 100mL bottle with two necks, add 30mL and be dried chlorobenzene and 20mL glacial acetic acid bottle with two necks, stirred overnight at room temperature.Pour into In 100mL water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with dichloromethane-petroleum ether as eluant, crosses post and separates, The black-and-blue solid of 0.16g, productivity is 80%.MALDI-TOFMS (m/z): C₁₁₀H₁₅₆N₄O₄S₁₃[M]⁺, theoretical value: 2013.85；Real Measured value: 2013.83

Its structural formula is as follows:

Embodiment 22

Under argon shield, fill the double thiophene three thienothiophene DFD3TBT (230mg, 0.20mmol) of dialdehyde base and The 50mL bottle with two necks of 25mL chloroform adds 0.8mL cyanoacetic acid n-octyl, under argon shield, is stirred at reflux overnight.Fall To room temperature, pouring in 100mL frozen water, dichloromethane (30mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) washing with water (100mL), anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether and the mixed liquor of dichloromethane (volume ratio 2: 1) is eluant, crosses post and separates.¹H NMR(400MHz,CDCl₃): 8.21 (s, 2H), 7.60 (s, 2H), 7.31 (m, 4H), 7.14 (d, J=3.6Hz, 2H), 7.07 (s, 2H), 3.64 (t, J=6.4Hz, 4H), 2.84 (t, J=7.6Hz, 4H), 2.79 (t, J=7.6Hz, 4H), 1.68 (m, 12H), 1.28 (m, 60H), 0.89 (m, 18H).

Its structural formula is as follows:

Embodiment 23

Under argon shield, cough up filling (147mg, 0.104mmol) double (aldehyde radical three thiophene) thiophene, the nitrile of ten times of molar equivalents Guanidine-acetic acid monooctyl ester and 50mL are dried in chloroform bottle with two necks and instill several triethylamines, stirred overnight at room temperature.Pour 100mL water into In, dichloromethane (20mL × 3) extracts.Organic phase washed with water (50mL), saturated aqueous common salt (50mL) and water (50mL) are washed, nothing Aqueous sodium persulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=1: 1 as eluant, crosses post and separates, obtain brown solid Body, productivity is 90%.MALDI-TOF MS (m/z): C₉₀H₁₂₄N₄O₆S₇[M]⁺, theoretical value: 1773.9；Measured value: 1773.9.

Its structural formula is as follows:

Embodiment 24

Under argon shield, filling (1.0g, 0.71mmol) 3T (BDT) 3T (CHO) 2, the itrile group second of ten times of molar equivalents Misery ester and 70mL are dried in chloroform bottle with two necks and instill several triethylamines, room temperature 40 hours.Pour in 100mL water, dichloro Methane (50mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) are washed, anhydrous sulfur Acid sodium is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=2: 3 as eluant, crosses post and separates, obtain black solid, produce Rate is 70%.MALDI-TOF MS (m/z): C₁₀₆H₁₄₈N₂O₄S₈[M]⁺, theoretical value: 1768.92；Measured value: 1768.93.

Its structural formula is as follows:

Embodiment 25

Under argon shield, filling the double thiophene of (173mg, 0.1mmol) double (aldehyde radical three thiophene) oxygen iso-octyl benzo, ten times The 3-ethyl Lip river tannin of molar equivalent and ammonium acetate (2mg, 0.012mmol), agitating heating refluxes overnight.Drop to room temperature, pour into In 200mL water, adding the extraction of 80mL dichloromethane, organic facies adds 80mL washing (three times).Organic facies anhydrous magnesium sulfate is dried, Filtering, be spin-dried for, with dichloromethane and petroleum ether (2: 1) as eluent, pillar layer separation, productivity is 70%, MALDI-TOF MS (m/z): C₉₄H₁₂₄N₂O₄S₁₂[M]⁺, theoretical value: 1728.62；Measured value: 1728.61.Its structural formula is as follows:

Embodiment 26

Under argon shield, cough up (170mg, 0.1mmol) filling double (aldehyde radical three thiophene) thiophene, the 3-second of ten times of molar equivalents Killough tannin (20mg, 0.12mmol) and ammonium acetate (20mg, 0.12mmol), agitating heating refluxes overnight.Drop to room temperature, pour into In 200mL water, adding the extraction of 80mL dichloromethane, organic facies adds 50mL washing (three times).Organic facies anhydrous magnesium sulfate is dried, Filter, be spin-dried for, with dichloromethane and petroleum ether (1: 1) as eluent, pillar layer separation, obtain brown solid, productivity is 82%, MALDI-TOF MS (m/z): C₉₂H₁₂₄N₂O₂S₁₃Si[M]⁺, theoretical value: 1701.61；Measured value: 1701.60.

Its structural formula is as follows:

Embodiment 27

Method is with embodiment 2.Replacing cyan-acetic ester with the third two eyeballs, productivity is 83%.MALDI-TOF MS (m/z): C₁₀₆H₁₄₈N₂O₄S₈[M]⁺, theoretical value: 1400.69；Measured value: 1400.69.

Its structural formula is as follows:

Under argon shield, filling intermediate HOC3T (BDT) 3TCHO (1.0g, 0.71mmol), ten times of molar equivalents Itrile group Caprylyl acetate and 70mL are dried in chloroform bottle with two necks and instill several triethylamines, room temperature 40 hours.Pour 100mL water into In, dichloromethane (50mL × 3) extracts.Organic phase washed with water (100mL), saturated aqueous common salt (100mL) and water (100mL) Washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=2: 3 as eluant, crosses post and separates, obtain black Color solid, productivity is 70%.MALDI-TOF MS (m/z): C₁₀₆H₁₄₈N₂O₄S₈[M]⁺, theoretical value: 1768.92；Measured value: 1768.93。

Its structural formula is as follows:

Embodiment 28

Under argon shield, filling (360mg, 0.2mmol) 3T (OEH-BDT) 3T (CHO)₂, the nitrile of ten times of molar equivalents Guanidine-acetic acid monooctyl ester and 100mL are dried in chloroform bottle with two necks and instill several triethylamines, stirred overnight at room temperature.Pour 100mL water into In, dichloromethane (30mL × 3) extracts.Organic phase washed with water (60mL), saturated aqueous common salt (60mL) and water (60mL) are washed, nothing Aqueous sodium persulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=1: 2 as eluant, crosses post and separates, obtain brown solid Body, productivity is 91%.MALDI-TOF MS (m/z): C₁₀₆H₁₄₈N₂O₄S₈[M]⁺, theoretical value: 1800.91；Measured value: 1800.90。

Its structural formula is as follows:

Embodiment 29

Under argon shield, filling intermediate 5T (OEH-BDT) 5T (CHO)₂(0.18g, 0.08mmol), works as ten times moles Itrile group Caprylyl acetate and the 60mL of amount are dried in chloroform bottle with two necks and instill several triethylamines, are stirred at room temperature 48 hours.Pour into In 100mL water, dichloromethane (50mL × 3) extracts.Organic phase washed with water (80mL), saturated aqueous common salt (80mL) and water (80mL) washing, anhydrous sodium sulfate is dried.Removal of solvent under reduced pressure, with petroleum ether-dichloromethane=2: 3 as eluant, crosses post and separates, Obtaining black solid, productivity is 76%.MALDI-TOF MS (m/z): C₁₅₄H₂₂₀N₂O₆S₁₂[M]⁺, theoretical value: 2577.36；Actual measurement Value: 2577.35.

Its structural formula is as follows:

Embodiment 30

Similar with the synthetic method of embodiment 14, simply substitute 3-ethyl Lip river tannin, reaction yield with 3-octyl group Lip river tannin 90%, MALDI-TOF MS (m/z): C₁₀₀H₁₄₅N₂O₂S₁₁[M]⁺, theoretical value: 1758.83；Measured value: 1758.82.

Its structural formula is as follows:

Embodiment 31

Similar with the synthetic method of embodiment 14, simply substitute 3-ethyl Lip river tannin, reaction yield with 3-methyl Lip river tannin 96%, MALDI-TOF MS (m/z): C₈₆H₁₁₈N₂O₂S₁₁[M]⁺, theoretical value: 1562.61；Measured value: 1562.62.

Its structural formula is as follows:

Embodiment 32

Similar with the synthetic method of embodiment 14, simply with 3T (DPP) 3T (CHO)₂Replace 7T (CHO) 2, reaction yield 76%, MALDI-TOF MS (m/z): C₈₂H₁₀₅N₃O₂S₁₁[M]⁺, theoretical value: 1547.50；Measured value: 1547.52.

Its structural formula is as follows:

Embodiment 33

Method is with embodiment 2, simply with 3T (DPP) 3T (CHO)₂Replace 7T (CHO) 2, reaction yield 76%, MALDI- TOF MS (m/z): C₈₂H₁₀₅N₃O₂S₁₁[M]⁺, theoretical value: 1547.50；Measured value: 1547.52.

Its structural formula is as follows:

Embodiment 34

Similar with the synthetic method of embodiment 14, simply with 5T (CHO)₂Replace 7T (CHO)₂, reaction yield 96%, MALDI-TOF MS (m/z): C₆₅H₉₀N₂O₂S₉[M]⁺, theoretical value: 1218.44；Measured value: 1218.45.

Its structural formula is as follows:

Embodiment 35

Similar with embodiment 14 synthetic method, 3-(1-acetyl triethyl) methyl Lip river tannin substitutes 3-ethyl Lip river tannin, reaction Yield 87%, MALDI-TOF MS (m/z): C₉₂H₁₂₆N₂O₆S₁₁[M]⁺, theoretical value: 1706.65；Measured value: 1706.64.

Its structural formula is as follows:

Embodiment 36

Method is with embodiment 2.With 1-semi-annular jade pendant acyl butyl-2,3,3-tri-methyl indole inner salts replace cyan-acetic ester, reaction Yield 87%, MALDI-TOF MS (m/z): C₁₀₆H₁₄₆N₂O₆S₉[M]⁺, theoretical value: 1830.86；Measured value: 1830.87.

Its structural formula is as follows:

Embodiment 37

Similar with the synthetic method of embodiment 14, replace 7T (CHO) with dialdehyde-based benzothiazole two thiophene₂, reaction yield 79%, MALDI-TOF MS (m/z): C₄₂H₅₀N₄O₂S₇[M]⁺, theoretical value: 866.19；Measured value: 866.19.

Its structural formula is as follows:

Embodiment 38

The heat stability testing to receptor type oligo-thiophenes containing receptor end group in embodiment 2 to 6

Containing receptor end group to the heat stability of receptor type oligo-thiophenes with thermogravimetric analysis (TG) at TA instrument Carrying out on SDT-TG Q600 thermogravimetric analyzer, means of differential scanning calorimetry (DSC) is on TA instrument DSC-2910 analyser It is analyzed.It is 10 DEG C/min that nitrogen flows down heat scan speed.

Embodiment 39

The cyclic voltammetry test of compound in embodiment 4 to 6

Molecular energy level structure is it will be seen that, to estimate highest occupied molecular orbital (HOMO) and minimum by cyclic voltammetry The size of the value of unoccupied orbital (LUMO).We use LK98B II electrochemical workstation to carry out the test of electrochemical properties, electrolysis Pond is three-electrode system (glass-carbon electrode is working electrode, and platinum electrode is auxiliary electrode, and calomel electrode is reference electrode), with two Cyclopentadienyl ferrum does internal standard, and dried dichloromethane is solvent, the tetrabutyl hexafluorophosphoric acid amine (n-Bu of 0.1M₄NPF₆) for supporting electrolysis Matter, scanning speed is 100mV s^-1.Under argon shield, the cyclic voltammetry curve that scanning obtains is as shown in Figure 3.By with reference to literary composition Offer (Li, Y.F.；Cao, Y.；Gao, J.；Wang, D.L.；Yu, G.；Heeger, A.J.Synth.Met.1999,99,243.) change Calculate and obtain HOMO and the lumo energy of molecule:

Embodiment 4:E (HOMO)=-5.09eV, E (LUMO)=-3.33eV.

Embodiment 5:E (HOMO)=-5.13eV, E (LUMO)=-3.29eV.

Embodiment 6:E (HOMO)=-5.10eV, E (LUMO)=-3.26eV.

Embodiment 40

The preparation of the solar cell device with the compound in embodiment 4 to 6 as electron donor

Device architecture is ITO/PEDOT:PSS/donor:PC₆₁BM/Ca/Al, the change during wherein donor is embodiment 4 to 6 Any one of compound.Concrete preparation process is: first ITO (tin indium oxide, anode) glass is carried out pretreatment, specifically walks Rapid as follows: first to clean ito glass with abluent, deionized water rinsing is clean, then by ito glass successively by acetone, isopropyl Each 20 minutes of alcoholic solvent ultrasonic cleaning, puts into after taking-up in baking oven and dries.Spin coating one layer on the most pretreated ito glass PEDOT:PSS (Baytron P VP Al4083), as anode modification layer (40nm), treats that PEDOT:PSS heats 20 points at 120 DEG C After clock is completely dried, by donor:PC₆₁Chloroformic solution (the donor:PC of BM mixture₆₁BM mass ratio is 1: 0.5, and donor is dense Degree is for 8mg/mL) it is spin-coated on PEDOT:PSS surface as active layer (140nm), it is deposited with Ca (20nm) and metal electrode the most again Al(80nm).Keep vacuum less than 4 × 10 during evaporation^-4Pa.Under standard sunlight (AM1.5G) radiation parameter, make Device performance is tested by the Keithley2400 digital sourcemeter computerizedd control.The current density voltage curve of device As shown in Figure 4, performance parameter is listed in table 1.

Table 1: compound solar cell Performance comparision prepared by embodiment 4,5,6 material

(light intensity is 100mW/cm²AM1.5G measures under the conditions of irradiating)

As shown in Table 1, the body heterojunction solar cell device that the solution utilizing the compound of the application to prepare processes Ultravioletvisible absorption can reach 800nm, solar device open-circuit voltage reaches more than 0.85V, and short circuit current reaches 9mA/ cm²Above, maximum photoelectric transformation efficiency can reach more than 5%.

Embodiment 41

Testing to the uv-vis spectra of receptor oligomerization thiophene containing receptor end group in embodiment 14

The compound of embodiment 14 is made into 10 respectively^-5With 10^-2The chloroformic solution of mol/L, it is purple that former solution measures solution Outer absorption, the latter solution is in 1200rpm rejection film on piezoid, and the uv absorption of measurement film, sweep limits is 300- 1000nm, measuring instrument is Jasco V-570UV/VIS/NIR Spectrophotometer.Ultraviolet-visible absorption spectroscopy such as figure Shown in 5.

Embodiment 42

The solution of the compound in embodiment 14 and the cyclic voltammetry test of film

Molecular energy level structure is it will be seen that, to estimate highest occupied molecular orbital (HOMO) and minimum by cyclic voltammetry The size of the value of unoccupied orbital (LUMO).We use LK98B II electrochemical workstation to carry out the test of electrochemical properties, electrolysis Pond is three-electrode system (glass-carbon electrode is working electrode, and platinum electrode is auxiliary electrode, and calomel electrode is reference electrode), solution Method does internal standard with ferrocene, and dried dichloromethane is solvent, the tetrabutyl hexafluorophosphoric acid amine (n-Bu of 0.1M₄NPF₆) for propping up Holding electrolyte, scanning speed is 100mV.s^-1；The electrochemistry of film with dry acetonitrile as solvent, the tetrabutyl hexafluorophosphoric acid of 0.1M Amine (n-Bu₄NPF₆) it is supporting electrolyte, the solution of the compound of embodiment 14 is dripped to film forming on glass-carbon electrode and measures.All exist Under argon shield, the cyclic voltammetry curve that scanning obtains is as shown in Figure 6.

By list of references (Li, Y.F.；Cao, Y.；Gao, J.；Wang, D.L.；Yu, G.；Heeger, A.J.Synth.Met.1999,99,243.) conversion obtains the solution of compound and HOMO and the LUMO energy of film of embodiment 14 Level:

The compound (in solution) of embodiment 14

E (HOMO)=-5.00eV E (LUMO)=-3.28eV

The compound (in film) of embodiment 14

E (HOMO)=-5.21eV E (LUMO)=-3.74eV

Embodiment 43

The preparation of the solar cell device with the compound in embodiment 14 as electron donor

Device architecture is ITO/PEDOT:PSS/donor:PC₆₁BM/LiF/Al, wherein donor is the chemical combination of embodiment 14 Thing.Concrete preparation process is: first ITO (tin indium oxide, anode) glass is carried out pretreatment, specifically comprises the following steps that and first use Ito glass cleaned by abluent, and deionized water rinsing is clean, then by ito glass successively with acetone, isopropanol solvent ultrasonic cleaning Each 20 minutes, put into after taking-up in baking oven and dry.One layer of PEDOT:PSS of spin coating on the most pretreated ito glass (Baytron P VP Al4083) as anode modification layer (40nm), treat PEDOT:PSS 140 DEG C heating 20 minutes completely dry After dry, by the compound of embodiment 14: PC after cooling₆₁Chloroformic solution (the compound of embodiment 14: the PC of BM mixture₆₁BM matter Amount ratio respectively 1: 0.8,1: 0.5,1；0.3, the compound concentration of embodiment 14 is 8mg/mL) it is spin-coated on PEDOT:PSS surface As active layer (80nm), then it is deposited with LiF (0.8nm) and metal electrode Al (60nm).Vacuum is kept during evaporation Less than 3 × 10^-4Pa.Under standard sunlight (AM1.5G) radiation parameter, use computer-controlled Keithley2400 numeral Device performance is tested by source table.The current density voltage curve of device is as it is shown in fig. 7, performance parameter is listed in table 2.

Table 2: in embodiment 14 than the solar cell properties of preparation, compound compares that (light intensity is to receptor with difference 100mW/cm²AM1.5G measures under the conditions of irradiating)

As shown in Table 2, the body heterojunction solar cell device that the solution utilizing the compound of the present invention to prepare processes Ultravioletvisible absorption can reach 780nm, solar device open-circuit voltage reaches more than 0.90V, and short circuit current reaches 14mA/ cm²Above, maximum photoelectric transformation efficiency can reach more than 6%.

Embodiment 44

The preparation of the solar cell device with the compound in embodiment 25 as electron donor with test device architecture is ITO/PEDOT:PSS/91:PC₇₁BM/LiF/Al.The cleaning of ito glass

Process and PSS-PEDOT spin coating is identical with embodiment 43.Treat that PEDOT:PSS heats 20 minutes completely at 140 DEG C After drying, by 91 after cooling: PC₇₁The chloroformic solution (91: PC of BM mixture₇₁BM mass ratio is respectively 1: 0.6, and 1: 0.8,1: 0.1) it is spin-coated on PEDOT:PSS surface as active layer (80nm), is then deposited with LiF (0.8nm) and metal electrode Al (60nm). Keep vacuum less than 3 × 10 during evaporation^-4Pa.Under standard sunlight (AM1.5G) radiation parameter, use computer Device performance is tested by the Keithley2400 digital sourcemeter controlled.The current density voltage curve of device such as Fig. 8 institute Showing, performance parameter is listed in table 3.

Table 3: in embodiment 25 than the solar cell properties of preparation, compound compares that (light intensity is to receptor with difference 100mW/cm²AM1.5G measures under the conditions of irradiating)

It addition, above-mentioned device active layers mixed process adds a small amount of polydimethylsiloxane (polydimethylsiloxane, PDMS) so that energy conversion efficiency is further increased to 7.46%, electric current density-electricity Line curve of buckling is shown in that Fig. 9, concrete numerical value are shown in Table 4.

Table 4: with compound-C in embodiment 25₇₁The solar energy of the most commensurability PDMS is added when PCBM (1: 0.8) is active layer Battery performance compares

Embodiment 45

In embodiment 13,17,21,23,24,27,28,29,30,34 and 35, compound is as organic sun of electron donor The preparation of energy battery device

Cleaning treatment and the PSS-PEDOT spin coating of ito glass are identical with embodiment 43.Treat that PEDOT:PSS adds at 140 DEG C After heat is completely dried for 20 minutes, by donor:PC after cooling₆₁The chloroformic solution of BM mixture is spin-coated on the conduct of PEDOT:PSS surface Active layer, is then deposited with LiF (0.8nm) and metal electrode Al (60nm).Keep vacuum less than 3 × 10 during evaporation^- ⁴Pa.Under standard sunlight (AM1.5G) radiation parameter, use computer-controlled Keithley2400 digital sourcemeter to device Performance is tested.The current density voltage curve of device is as shown in Figure 10-21, and performance parameter is listed in table 5.

Table 5: in embodiment 13,17,21,23,24,27,28,29,30,34 and 35 compound as donor prepare organic Solar cell properties parameter

From the foregoing, it will be observed that utilize body heterojunction solar cell device that solution prepared by the compound of the present invention processes Big photoelectric transformation efficiency can reach more than 7%.And the compound of the present invention has accurate molecular weight, structure-controllable, Yi Chun Change, it is adaptable to preparation has high open circuit voltage, good stability, flexibility, large-area high-performance organic solar batteries.

Although being appreciated that in order to the purpose of exemplary illustration describes specific embodiments of the present invention from the foregoing, But under condit without departing from the spirit and scope of the present invention, technical staff described in this area may be made that various deformation or changes Enter.These deformation or amendment all should fall into the application scope of the following claims.

Claims

1. selected from formula (1) to formula (6) to receptor type oligo-thiophenes compound:

Wherein, n is the integer of 1 to 50,

R₁And R₂Separately selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or its The derivant of halogen substiuted, wherein R₁And R₂Can be the same or different, but R₁And R₂Can not be H simultaneously,

D and D₁Separately selected from group 7 to group 19:

Wherein R₃Selected from H, C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Carboxylic acid ester groups or its halogen substiuted Derivant；

A and A₁Separately selected from group 21 to group 30:

Wherein R₄Selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Alkoxyl, C₁-C₃₀Spreading out of carboxylic acid ester groups or its halogen substiuted Biological；And

A₂For end group by body unit and selected from group 31 to group 54 and group 56 to group 60:

Wherein R₅And R₆Separately selected from C₁-C₃₀Alkyl, C₃-C₃₀Cycloalkyl, C₁-C₃₀Spreading out of alkoxyl or its halogen substiuted Biology, and

X^-For A can be made₂Form the anion of neutral group.

2. compound as claimed in claim 1, the structure of wherein said compound is selected from:

Wherein, n is the integer of 1 to 50,

3. compound as claimed in claim 1 or 2, wherein n is the integer of 1 to 30.

4. compound as claimed in claim 3, wherein n is the integer of 1 to 10.

5. compound as claimed in claim 1 or 2, wherein X^-Selected from halide ion, BF₄ ^-、PF₆ ^-、SO₃ ^-Or CF₃SO₃ ^-。

6. compound as claimed in claim 1 or 2, it is selected from:

7. the method for compound described in any claim in preparation claim 1-6, wherein, donor bridging containing receptor end group Oligo-thiophenes by the oligo-thiophenes of dialdehyde base donor bridging and receptor end monomers, in the presence of solvent and catalyst, Carry out Ke Neifeinageer (Knoevenagel) condensation reaction, obtain described compound.

8. method as claimed in claim 7, wherein said catalyst is alkali compounds.

9. method as claimed in claim 8, wherein said alkali compounds is alkylamine.

10. method as claimed in claim 9, wherein said alkylamine is triethylamine.

11. methods as claimed in claim 7 or 8, wherein said method is carried out under a shielding gas.

12. methods as claimed in claim 11, wherein said protective gas is argon.

The method of compound described in any claim in 13. preparation claim 1-6, wherein, donor bridging containing little molecule The oligo-thiophenes of dyestuff end group is by the oligo-thiophenes of dialdehyde base donor bridging and organic molecule dye monomer, at solvent with urge In the presence of agent, carry out Ke Neifeinageer (Knoevenagel) condensation reaction, obtain described compound.

14. methods as claimed in claim 13, wherein said catalyst is acidic catalyst.

15. methods as claimed in claim 14, wherein said acidic catalyst is acidulous catalyst.

16. method as claimed in claim 15, wherein said acidulous catalyst is ammonium acetate, propanoic acid ammonium or butanoic acid ammonium.

17. methods as described in claim 13 or 14, wherein said solvent is acid solution.

18. methods as claimed in claim 17, wherein said acid solution is weakly acidic solution.

19. methods as claimed in claim 18, wherein said weakly acidic solution is acetic acid, propanoic acid or butanoic acid.

20. methods as claimed in claim 19, the consumption of wherein said catalyst is excess.

21. methods as claimed in claim 20, the consumption of wherein said catalyst is 10-30mol%.

22. methods as claimed in claim 20, the consumption of wherein said catalyst is 20mol%.

23. in claim 1-6 described in any claim containing receptor end group to receptor type oligo-thiophenes compound system Purposes in standby photovoltaic device.

24. purposes as claimed in claim 23, wherein said photovoltaic device is solar cell device.

25. purposes as claimed in claim 24, wherein said compound is lived for the light preparing described solar cell device Property layer.

26. triode device, it comprises the active layer in claim 1-6 with the compound described in any claim.

27. photovoltaic devices, it comprises the active layer in claim 1-6 with the compound described in any claim.

28. photovoltaic devices as claimed in claim 27, wherein said photovoltaic device is solar cell device.

29. methods preparing field-effect transistor, it include providing in claim 1-6 described in any claim containing receptor End group to receptor type oligo-thiophenes compound.

30. methods preparing photovoltaic device, it include providing in claim 1-6 described in any claim containing receptor end group To receptor type oligo-thiophenes compound.

31. methods as claimed in claim 30, wherein said photovoltaic device is solar cell device.

32. methods as claimed in claim 31, the light wherein providing described compound to prepare described solar cell device is lived Property layer.

33. compounds, it is selected from: