CN103804652A - Seleno[3,2-b]selenophen-benzodi(benzothiadiazole) containing copolymer as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a seleno[3,2-b]selenophen-benzodi(benzothiadiazole) containing copolymer as well as a preparation method and application thereof. The copolymer has a structure shown in a formula (I) in the specification and is prepared through Suzuki coupling reaction between benzodi(benzothiadiazole) and seleno-selenophen. The polymer consisting of the compounds seleno[3,2-b]selenophen and benzodi(benzothiadiazole) can form a strong donor-receptor structure, which is beneficial to improvement of the material stability and reduction of the material band gap, thus widening the sunlight absorption range and improving the photoelectric conversion efficiency.

Description

Contain also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer and its preparation method and application

Technical field

The invention belongs to organic materials technical field, specifically, the present invention relates to a kind of also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer and its preparation method and application that contains.

Background technology

The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell, because complex manufacturing, cost are high, is restricted its application at present.In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C ₆₀between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.The absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, is another major reason that causes energy transfer efficiency low.For further improving the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor on the one hand, raising absorbs sun power, can adopt on the other hand annealing, add the materials such as tensio-active agent to be optimized device.

Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.

Luxuriant and rich with fragrance by three six-rings one-tenth, all atoms are in same plane, there is good electronics cavity transmission ability, and the rigidity of molecule is conducive to improve the thermal stability of material, and luxuriant and rich with fragrance 9, easily modify for 10, can utilize easy method to introduce electron-donating group and electron-accepting group, regulate its confession/electrophilic performance.Therefore it has a wide range of applications in the photoelectric materials such as Organic Light Emitting Diode, organic solar batteries, field-effect transistor

The radius ratio sulphur atom of selenium atom large, can strengthen molecule between polymer poly compound chain overlapping more, promotes the hopping process of electric charge.Because selenophen has low band gap and 2,3,4,5 easily modify and replace, and have caused in recent years the very big concern of researcher.And also selenophen analog derivative has narrower being with than thiophthene analog derivative, be widely used in now in the photoelectric materials such as organic solar batteries, Organic Light Emitting Diode and field-effect transistor.

But the polymkeric substance that contains also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer does not still have document and patent report at present simultaneously, this has just limited its range of application greatly.Therefore, the present invention has developed and has contained also [3,2-b] two selenophens-benzo two (diazosulfide) conjugated polymers, expands their ranges of application in fields such as polymer solar batteries.

Summary of the invention

Based on this, the object of this invention is to provide a kind of also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains.

Concrete technical scheme is as follows:

A kind of also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains, described multipolymer has the structure of formula I,

Wherein, R ₃, R ₄for H or C ₁~ C ₂₀alkyl, R ₁, R ₂for C ₁~ C ₂₀alkyl; N is the integer between 1-100.

Therein in some embodiment, described R ₁, R ₂for C ₁~ C ₁₀alkyl, described R ₃, R ₄for C ₁~ C ₈alkyl; Described n is the integer between 25 ~ 75.

Another object of the present invention is to provide the above-mentioned also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains.

Concrete technical scheme is as follows:

A kind of also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains, comprises the steps:

(1), in inert gas environment, by structural formula be

4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, structural formula be

acetylene compound, catalyzer 1 and alkali 1 join in solvent 1,130 ℃ reaction 4h, obtain compound 3, the structural formula of described compound 3 is

Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are 1:2 with the mole dosage ratio of acetylene compound;

(2) in inert gas environment, compound 5 is added in solvent 2 ,-78 ℃ add butyllithium (t-BuLi) reaction 1-2h, then add tributyltin chloride (SnBu ₃cl), after-78 ℃ of reaction 1h, be warming up to room temperature, continue, after reaction 6h, to obtain compound 4 through neutral alumina column chromatography, the structural formula of described compound 5 is

the structural formula of described compound 4 is

Described compound 5 is 1:2 with the mole dosage ratio of butyllithium, described SnBu ₃the mole dosage of Cl is 2 times of compound 5;

(3) in inert gas environment, compound 3, compound 4, catalyzer 2, alkali 2 are added in solvent 3,50-120 ℃ is reacted 6 ~ 108 hours, described compound 3 is 1:1.5 ~ 1.5:1 with the mole dosage ratio of compound 4, obtain and contain also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer;

In above-mentioned corresponding formula, R ₃, R ₄for H or C ₁~ C ₂₀alkyl, R ₁, R ₂for C ₁~ C ₂₀alkyl; N is the integer between 1-100.

In some embodiment, in step (1), described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are to adopt following steps to make therein:

By structural formula be

compd E add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is

compound F 17-hydroxy-corticosterone;

Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is

compound G;

Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be

compound H;

Compound H is added to SnCl ₂in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

In some embodiment, in step (1), described alkali 1 is Bu therein ₃n, described alkali 1 is 1:1 with the mole dosage ratio of acetylene compound.

In some embodiment, described catalyzer 1 is palladium (Pd (OAc) therein ₂), the mole dosage of described catalyzer 1 is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

In some embodiment, in step (3), described catalyzer 2 is tetrakis triphenylphosphine palladium (Pd (PPh therein ₃) ₄), the mole dosage of described catalyzer 2 is the 0.05%-20% of compound 3; Described alkali 2 is Na ₂cO ₃, the amount of substance of described alkali 2 is 2-20 times of compound 4.

In some embodiment, solvent 1 described in step (1) is DMF (DMF) therein; Solvent 2 described in step (2) is tetrahydrofuran (THF) (THF); Described in step (3), solvent 3 is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.

In some embodiment, described rare gas element is nitrogen or helium therein.

The present invention also provide above-mentioned containing [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer also at polymer solar battery, organic electroluminescent, organic field effect tube, the application in organic optical storage and organic laser field.

Major advantage of the present invention is:

1, the route of synthetic benzo two (diazosulfide) is fairly simple and ripe, easily improves solvability and the molecular weight of product by introducing alkyl, is conducive to film forming processing;

2, benzo two (diazosulfide) is a kind of very excellent donor material, benzo two (diazosulfide) has simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, by compound also [3, 2-b] two selenophens, the polymkeric substance that benzo two (diazosulfide) forms can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand sunlight absorption region, improve electricity conversion,

3, Suzuki reaction is a kind of very ripe polyreaction, and productive rate is high, and mild condition, is easy to control.

Accompanying drawing explanation

Fig. 1 is the structural representation using the multipolymer of the embodiment of the present invention as the organic solar batteries device of active coating;

Fig. 2 is the structural representation using the multipolymer in the embodiment of the present invention 1 as the organic electroluminescence device of luminescent layer.

Embodiment

In order to understand better the content of patent of the present invention, further illustrate the present invention below by concrete example and accompanying drawing, but these embodiments do not limit the present invention.

Involved in the present invention containing [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer also, there is following structure:

In formula: R ₃, R ₄for H or C ₁~ C ₂₀alkyl, R ₁, R ₂for C ₁~ C ₂₀alkyl; N is the integer between 1-100.

Preferably, described R ₁, R ₂for C ₁～C ₁₀alkyl, described R ₃, R ₄for C ₁～C ₈alkyl; Described n is the integer between 25 ~ 75.

More preferably, described R ₁, R ₂for C ₁₀alkyl, described R ₃, R ₄for C ₈alkyl; Described n is 34.

A kind of also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains of the present invention, comprises the steps:

(1) in inert gas environment, by 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, acetylene compound, catalyzer 1 and alkali 1 join in solvent 1, and 130 ℃ of reaction 4h, obtain compound 3, and the structural formula of described compound 3 is

The reaction equation of this step is as follows:

Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are with the mole dosage of acetylene compound than being 1:2, and described alkali 1 is Bu ₃n, described alkali 1 is 1:1 with the mole dosage ratio of acetylene compound; Described catalyzer 1 is Pd (OAc) ₂, the mole dosage of described catalyzer 1 is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides; Described solvent 1 is DMF.

(2) in inert gas environment, compound 5 is added in solvent 2 ,-78 ℃ add butyllithium reaction 1-2h again, then add SnBu ₃cl, after-78 ℃ of reaction 1h, is warming up to room temperature, continues, after reaction 6h, to obtain compound 4 through neutral alumina column chromatography, and the structural formula of described compound 5 is

the structural formula of described compound 4 is

The reaction equation of this step is as follows:

Described compound 5 is 1:2 with the mole dosage ratio of butyllithium, described SnBu ₃the mole dosage of Cl is 2 times of compound 5; Described solvent 2 is THF.

(3) in inert gas environment, compound 3, compound 4, catalyzer 2, alkali 2 are added to the Suzuki coupling reaction carrying out in solvent 3,50-120 ℃ is reacted 6 ~ 100 hours, obtains and contains also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer.

The reaction equation of this step is as follows:

Described compound 3 is 1:1.5 ~ 1.5:1 with the mole dosage ratio of compound 4; Described catalyzer 2 is Pd (PPh ₃) ₄, the mole dosage of described catalyzer 2 is the 0.05%-20% of compound 3; Described alkali 2 is Na ₂cO ₃, the amount of substance of described alkali 2 is 2-20 times of compound 4, described solvent 3 is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.

In above-mentioned steps, described rare gas element is nitrogen or argon gas.

Following examples contribute to understand the present invention, but do not limit the scope of the invention.

Embodiment 1: the preparation of poly-{ 3,6-dioctyl is [3,2-b] two selenophen-6 also, 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

1, compound 5-nitro-2,1,3 diazosulfide

In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride, stir and slowly drip 2ml pyridine, after heating, in 80 ~ 90 ℃ of back flow reaction 24h, stopped reaction, is heated to 80 ℃ and revolves and steam excessive SOCl ₂after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%;

2, compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide

In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide 15ml, be warming up to 127 ℃ of backflows, in 30min, slowly drip bromine 11.3ml the 4h that refluxes, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 10.2g, productive rate: 50%

3,4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides

In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF DMF of 90ml, was heated to 120 ℃ of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%;

4,4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

In there-necked flask, add 4,4 '-bis-bromo-ly 6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), add the tetrahydrofuran THF that 300ml is dry, add 40g SnCl ₂(200mmol), be warming up to 100 ℃, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtains solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20ml(37.7mmol in 30 minutes), temperature is controlled at below 5 ℃, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide+100ml water) to vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.Two, compound 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides)

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), add 2,6,13,17-tetramethyl--9-octadecyne (3.07g, 10mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 25ml DMF, pass into nitrogen gas stirring 20min, add Bu3N (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filters, underpressure distillation, silica gel column chromatography separates, and obtains 2.4g product 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 70%.

Product 4,9-bis-is bromo-6, and the structured testing data of 7-bis-(3,7-dimethyl) octyl group benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.32（d，2H），3.08（dd，4H），1.83（d，2H），1.60-1.64（m，6H），1.22-1.27（m，12H）,1.08-1.10（m，18H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：134.0,131.8,130.2,129.9,124.9,123.6,130.0,41.0,39.7,38.0,32.6,28.5,25.6,24.2,23.0,21.0；

Three, 3,6-dioctyl-2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Under the protection of nitrogen; in there-necked flask, add 3; 6-dioctyl-2,5-dibromo selenophen (6.16g, 0.01mol); add the tetrahydrofuran solvent of 80ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL, 2.5M, 0.02mol) with syringe again; continue stirring reaction 2h, under-78 ℃ of conditions, inject SnBu with syringe ₃cl (5.6mL, 0.02mol), stirs and spends the night under room temperature.Add saturated sodium-chloride water solution (30ml) termination reaction, with chloroform extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina chromatographic separation, obtain product, productive rate 75%.

Four, poly-{ 3,6-dioctyl is [3,2-b] two selenophen-6 also, 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection, add 3,6-dioctyl-2; 5-bis-(tributyl tin) also [3; 2-b] two selenophens (207.4mg, 0.2mmol), 4,9-bis-bromo-6; 7-bis-(3; 7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfide) (146.6mg; 0.2mmol), with toluene solvant 40ml, then add 5mg(0.0043mmol) Pd (PPh ₃) ₄, solution is heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

By the polymer poly after purifying, { 3,6-dioctyl is [3,2-b] two selenophen-6 also, 7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (P1) carry out GPC test, number-average molecular weight Mn ≈ 52950, n=50, polymkeric substance monodispersity is 2.3.

Embodiment 2: the preparation of poly-{ also [3,2-b] two selenophen-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1

Two, compound 4,9-bis-is bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides)

Prepare 4,9-bis-with embodiment 1 step 2 bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (diazosulfides).

Three, 2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Under the protection of nitrogen; in there-necked flask, add 2; 5-dibromo is [3,2-b] two selenophens (7.84g, 0.02mol) also; add the tetrahydrofuran solvent of 80ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (16.8mL, 2.5M, 0.04mol) with syringe again; continue stirring reaction 2h, under-78 ℃ of conditions, inject SnBu with syringe ₃cl (11.2mL, 0.04mol), stirs and spends the night under room temperature.Add saturated sodium-chloride water solution (30ml) termination reaction, with chloroform extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina chromatographic separation, obtain product, productive rate 65%.

Four, the preparation of poly-{ also [3,2-b] two selenophen-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection, add 2,5-bis-(tributyl tin) also [3; 2-b] two selenophen (243.6mg; 0.3mmol), 4,9-bis-is bromo-6,7-bis-(3; 7-dimethyl octyl group)-benzo [2; 1-e:3,4-e] two (diazosulfide) (146.6mg, 0.2mmol) and toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 6.25mg(0.0054mmol) Pd (PPh ₃) ₄, 2M 1.5ml Na ₂cO ₃(2mmol) be heated to 120 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross silica gel column chromatography, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.

By polymer poly { also [3,2-b] two selenophen-6,7-bis-(3 after purifying, 7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (diazosulfides) } (P2) carry out GPC test, number-average molecular weight Mn ≈ 28390, n=34, polymkeric substance monodispersity is 2.2.

Embodiment 3: the preparation of poly-{ 3,6-dioctyl is [3,2-b] two selenophens-6-(2 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1.

Two, 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfides)

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol) and 2,6 – dimethyl-9-30 alkynes (4.47g, 10mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 25mlDMF, passes into nitrogen gas stirring 20min, adds Bu ₃n (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 2.7g product 4, the bromo-6-bis-of 9-bis-(2,7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 62%.

Gained 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) the structured testing data of octyl group-7-NSC 62789 base-benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.30（d，2H），3.01（m，4H），1.85(s,1H)，1.60-1.65(m,5H),1.25-1.34（m，40H），1.01-1.07（m，12H）；

¹³CNMR（CDCl ₃）δ（TMS，ppm）：134.0，131.9，130.3，130.1，129.9，124.9，123.8，41.5,39.9,37.8，32.8，32.2，31.9，31.6，29.7，29.3，28.5,28.1，24.2，23.0，22.7，21.0，14.3。

Three, 3,6-dioctyl-2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Prepare 3,6-dioctyl-2 with embodiment 1 step 3,5-bis-(tributyl tin) is [3,2-b] two selenophens also.

Four, gather 3,6-dioctyl is [3,2-b] two selenophens-6-(2 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides)

Under nitrogen protection, in reactor, add 3,6-dioctyl-2; 5-bis-(tributyl tin) is [3,2-b] two selenophens (259.3mg, 0.25mmol) also; 4; the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-ceryl-benzo [2,1-e:3; 4-e] two (diazosulfide) (359.0mg; 0.375mmol), with tetrahydrofuran (THF) 50ml, vacuumize deoxygenation and be filled with nitrogen, then add 43.2mg(0.0374mmol) Pd (PPh ₃) ₄, be heated to 120 ℃ of reactions 4.5 days.After reaction, in reactor, add deionized water 20ml and toluene 40ml to extract, get organic phase, underpressure distillation is to about 6.5ml left and right, splashed in 500ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, suction filtration, after oven dry, obtain pressed powder, pressed powder is dissolved with chloroform, separate with silica gel column chromatography, organic solvent is removed in decompression, with suction filtration after methyl alcohol sedimentation, gained solid is used acetone extraction three days in apparatus,Soxhlet's, use again methyl alcohol sedimentation, suction filtration, vacuum pump suction filtration spends the night, obtain product poly-{ 3, 6-dioctyl also [3, 2-b] two selenophens-6-(2, 7-dimethyl) octyl group-7-eicosyl-benzo [2, 1-e:3, 4-e] two (diazosulfides) }.

By the polymer poly { 3 after purifying, 6-dioctyl also [3,2-b] two selenophens-6-(2,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) } (P3) carry out GPC test, number-average molecular weight Mn ≈ 90000, n=75, polymkeric substance monodispersity is 2.9.

Embodiment 4: the preparation of poly-{ also [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1.

Two, 4, the bromo-6-methyl-7-of 9-bis-ethyl benzo [2,1-e:3,4-e] two (diazosulfides)

In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (6.8g, 10mmol), add valerylene (1.36g, 20mmol) (synthetic method is with reference to Chem.Commun., and 2011,47,8850-8852), 50ml DMF, passes into nitrogen gas stirring 20min, adds Bu ₃n (1.814g, 20mmol) and Pd (OAc) ₂(230mg, 1.0mmol), is warming up to 130 ℃, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, obtain 2.6g product 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides), productive rate 52.6%.

Product 4, the structured testing data of the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) are as follows:

¹HNMR（CDCl ₃）δ（TMS，ppm）：8.31（d，2H），3.03（d，2H），2.67(s,3H)，1.35（d，3H）;

¹³CNMR（CDCl ₃）δ（TMS，ppm）：135.0，131.8，130.5，130.0，129.7，124.9，123.5，24.5，16.8，15.5。

Three, 2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Prepare also [3,2-b] two selenophens of 2,5-bis-(tributyl tin) with embodiment 2 step 3.

Four, the preparation of poly-{ also [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) }

Under nitrogen protection; add 2; 5-bis-(tributyl tin) is [3,2-b] two selenophens (162.4mg, 0.2mmol), 4 also; the bromo-6-methyl-7-of 9-bis-ethyl benzo [2; 1-e:3,4-e] two (diazosulfide) (148.2mg, 0.3mmol) and toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 0.173mg(0.00015mmol) Pd (PPh ₃) ₄, be heated to 50 ℃ of reaction 6h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross silica gel column chromatography, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product poly-{ also [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) }.

Polymer poly { also [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) } after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 596, n=1.

Embodiment 5: poly-3,6-dimethyl is [3,2-b] two selenophens-6-(2 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1.

Two, 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides)

Prepare the bromo-6-(3 of 4,9-bis-, 7-dimethyl with embodiment 3 step 2) octyl group-7-NSC 62789 base benzo [2,1-e:3,4-e] two (diazosulfides).

Three, 3,6-dimethyl-2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Under the protection of nitrogen; in there-necked flask, add 3; 6-dimethyl-2,5-dibromo selenophen (8.40g, 0.02mol); add the tetrahydrofuran solvent of 100ml; under-78 ℃ of conditions, slowly inject n-Butyl Lithium (16.8mL, 2.5M, 0.04mol) with syringe again; continue stirring reaction 2h, under-78 ℃ of conditions, inject SnBu with syringe ₃cl (11.2mL, 0.04mol), stirs and spends the night under room temperature.Add saturated sodium-chloride water solution (30ml) termination reaction, with chloroform extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to neutral alumina chromatographic separation, obtain product, productive rate 70%.

Four, gather 3,6-dimethyl is [3,2-b] two selenophens-6-(3 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides)

Under nitrogen protection; add 3,6-dimethyl-2,5-bis-(tributyl tin) also [3; 2-b] two selenophen (168mg; 0.2mmol), 4, the bromo-6-(3 of 9-bis-, 7-dimethyl) octyl group-7-NSC 62789 base benzo [2; 1-e:3; 4-e] two (diazosulfide) (146.6mg, 0.2mmol) and toluene solvant 40ml, then add 6.25mg(0.0054mmol) Pd (PPh ₃) ₄, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product poly-{ 3,6-dimethyl is [3,2-b] two selenophens-6-(3 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) }.

By the polymer poly after purifying, { 3,6-dimethyl is [3,2-b] two selenophens-6-(3 also, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) } carry out GPC test, number-average molecular weight Mn ≈ 35105, n=35, polymkeric substance monodispersity is 2.7.

Embodiment 6: poly-{ 3,6-bis-(NSC 62789 base) is [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) also }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1.

Two, 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides)

Prepare the bromo-6-methyl-7-of 4,9-bis-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) with embodiment 4 step 2.

Three, 3,6-bis-(NSC 62789 base)-2,5-bis-(tributyl tin) is [3,2-b] two selenophens also

Under the protection of nitrogen; in there-necked flask, add 3,6-bis-(NSC 62789 base)-2,5-dibromo also [3; 2-b] two selenophen (9.53g; 0.01mol), add the tetrahydrofuran solvent of 100ml, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8.4mL with syringe again; 2.5M; 0.02mol), continue stirring reaction 2h, under-78 ℃ of conditions, inject SnBu with syringe ₃cl (5.6mL, 0.02mol), stirs and spends the night under room temperature.Add saturated sodium-chloride water solution (30ml) termination reaction, with chloroform extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate 68%.

Four, poly-{ 3,6-bis-(NSC 62789 base) is [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) also }

Under nitrogen protection; add 3,6-bis-(NSC 62789 base)-2,5-bis-(tributyl tin) also [3; 2-b] two selenophen (274.6mg; 0.2mmol), 4, the bromo-6-methyl-7-of 9-bis-ethyl-benzo [2,1-e:3; 4-e] two (diazosulfide) (98.8mg; 0.2mmol), with toluene solvant 40ml, vacuumize deoxygenation and be filled with nitrogen, then add 46.16mg(0.0399mmol) Pd (PPh ₃) ₄, be heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 6ml left and right, splashed in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product poly-{ 3,6-bis-(NSC 62789 base) is [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (diazosulfides) also }.

By the polymer poly after purifying, { 3,6-bis-(NSC 62789 base) is [3,2-b] two selenophens-6-methyl-7-ethyl-benzo [2 also, 1-e:3,4-e] two (diazosulfides) } carry out GPC test, number-average molecular weight Mn ≈ 28950, n=25, polymkeric substance monodispersity is 3.2.

Embodiment 7: poly-also [3,2-b] two selenophens-6-(2 of 3,6-bis-(NSC 62789 base), 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) }

One, 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides

With embodiment 1 step 1.

Two, 4, the bromo-6-(2 of 9-bis-, 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides)

Prepare the bromo-6-(2 of 4,9-bis-, 7-dimethyl with embodiment 3 step 2) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides).

Three, 3,6-bis-(NSC 62789 base)-2,5-bis-(tributyl tin)

Same embodiment 6 step 3 prepare 3,6-bis-(NSC 62789 base)-2,5-bis-(tributyl tin).

Four, gather also [3,2-b] two selenophens-6-(2 of 3,6-bis-(NSC 62789 base), 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides)

Under nitrogen protection, add 3,6-bis-(NSC 62789 base)-2; 5-bis-(tributyl tin) also [3; 2-b] two selenophens (274.6mg, 0.2mmol), 4, the bromo-6-(2 of 9-bis-; 7-dimethyl) octyl group-7-eicosyl-benzo [2; 1-e:3,4-e] two (diazosulfide) (174.6mg, 0.2mmol) and toluene solvant 40ml; vacuumize deoxygenation and be filled with nitrogen, then add 5mg(0.0043mmol) Pd (PPh ₃) ₄, be heated to 90 ℃ of reaction 100h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 8ml left and right, splashed in 450ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product poly-{ also [3,2-b] two selenophens-6-(2 of 3,6-bis-(NSC 62789 base), 7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) }.

By the polymer poly { 3 after purifying, 6-bis-(NSC 62789 base) also [3,2-b] two selenophens-6-(2,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (diazosulfides) } carry out GPC test, number-average molecular weight Mn ≈ 153600, n=100, polymkeric substance monodispersity is 4.5.

Embodiment 8, the multipolymer of preparing take the embodiment of the present invention are active coating, prepare organic solar cell device, and its structure as shown in Figure 1, comprises the substrate of glass stacking gradually, anode, middle supplementary layer, active coating and negative electrode.Wherein, anode is ITO, is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and middle supplementary layer adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, be called for short PEDOT:PSS(CLEVIOS P VPAl 4083); Active coating comprises electron donor material and electron acceptor material, and electron donor material is polymkeric substance prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C61-methyl-butyrate (being called for short PCBM); Negative electrode is aluminium, and this device architecture can briefly be described as glass/ITO/PEDOT:PSS/ active coating/Al.

Wherein, substrate of glass, as bottom, is chosen ito glass (with anode ITO layer, can buy, the ito glass in this embodiment is purchased from China Nanbo Group Co) when making, and thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 120nm; The multipolymer of again being prepared by the 10mg embodiment of the present invention is dissolved in 0.4ml dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4ml chlorobenzene obtains, and is spun on PEDOT:PSS rete, and thickness is about 100nm, obtains active coating; At vacuum condition (2 × 10 ^-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains organic solar batteries device.Preparation method and the structure of the organic solar batteries device that contains multipolymer of the present invention are not limited to the present embodiment, can device suitably be improved or be modified.

Prepared organic solar batteries device using the multipolymer of embodiment 1,2 and 3 preparations as active layer material respectively, obtained device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.

By the I-E characteristic of Keithley236 current/voltage source-measuring system and test component, obtain the performance data of device in table 1.

The performance data of the organic solar batteries device that table 1 is prepared take multipolymer of the present invention as active coating

As seen from the data in Table 1, the energy conversion efficiency of the organic solar batteries device of preparing as active coating with multipolymer of the present invention is 1.22 ~ 1.73, and report poly-[2, 7-(9, 9-di-n-octyl) fluorenes-5, 5 '-(4, 7-bis-selenophen-2, 2 '-yl)-2, 1, 3-selenole] effciency of energy transfer be that 0.432%(refers to (South China Science & Engineering University's journal (natural science edition), in February, 2005, the 2nd phase, the 33rd volume, 6-10 page), show of the present invention containing also [3, 2-b] two selenophens-benzo two (diazosulfide) multipolymer is owing to containing new benzo two (diazosulfide) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.

Embodiment 9, to the preparation containing the organic electroluminescence device of polymkeric substance of the present invention, its structure as shown in Figure 2:

The copolymer 1 of preparing take embodiment 1 is luminescent layer, is prepared with organic electroluminescence devices, and its structure as shown in Figure 2, comprises the glass substrate stacking gradually, transparent anode, luminescent layer, cathode buffer layer, negative electrode.Wherein, transparent anode be square resistance be 10-20 Ω/mouth tin indium oxide (ITO) (150nm), buffer layer adopts PEDOT:PSS(CLEVIOS P VP Al 4083) preparation (30nm), luminescent layer is copolymer 1 (90nm) prepared by the embodiment of the present invention 1, buffer layer is LiF (1.5nm), negative electrode is metal A l (150nm), and the structure of device is: ITO/PEDOT:PSS/ copolymer 1/LiF/Al, but the structure of practical devices is not limited to this.

Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 11.8cd/A, and high-high brightness is 1170cd/m ².

The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. one kind contains also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer, it is characterized in that, described multipolymer has the structure of formula I,

Wherein, R ₃, R ₄for H or C ₁~ C ₂₀alkyl, R ₁, R ₂for C ₁~ C ₂₀alkyl; N is the integer between 1-100.

2. also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 1, is characterized in that described R ₁, R ₂for C ₁~ C ₁₀alkyl, described R ₃, R ₄for C ₁～C ₈alkyl; Described n is the integer between 25 ~ 75.

Described in a claim 1 or 2 containing the preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer also, it is characterized in that, comprise the steps:

(1), in inert gas environment, by structural formula be

4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, structural formula be

acetylene compound, catalyzer 1 and alkali 1 join in solvent 1,130 ℃ reaction 4h obtain compound 3, the structural formula of described compound 3 is

Described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are 1:2 with the mole dosage ratio of acetylene compound;

(2) in inert gas environment, compound 5 is added in solvent 2 ,-78 ℃ add butyllithium, reaction 1-2h, then add SnBu ₃cl, after-78 ℃ of reaction 1h, is warming up to room temperature, continues, after reaction 6h, to obtain compound 4 through neutral alumina column chromatography, and the structural formula of described compound 5 is

the structural formula of described compound 4 is

Described compound 5 is 1:2 with the mole dosage ratio of butyllithium, described SnBu ₃the mole dosage of Cl is 2 times of compound 5;

(3) in inert gas environment, compound 3, compound 4, catalyzer 2, alkali 2 are added in solvent 3,50-120 ℃ is reacted 6 ~ 108 hours, described compound 3 is 1:1.5 ~ 1.5:1 with the mole dosage ratio of compound 4, obtain and contain also [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer;

In above-mentioned corresponding formula, R ₃, R ₄for H or C ₁~ C ₂₀alkyl, R ₁, R ₂for C ₁~ C ₂₀alkyl; N is the integer between 1-100.

4. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, in step (1), described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides are to adopt following steps to make:

By structural formula be compd E add in thionyl chloride, stir and drip pyridine in thionyl chloride, back flow reaction at 85 ℃, makes structural formula and is

compound F 17-hydroxy-corticosterone;

Compound F 17-hydroxy-corticosterone is added in Hydrogen bromide, and at 127 ℃, back flow reaction, after 30 minutes, is added dropwise to bromine, continues to reflux, and obtains structural formula and is compound G;

Compound G is added in the DMF solvent that copper powder catalyst exists, be heated to react 3 hours at 120 ℃, obtain structural formula and be

compound H;

Compound H is added to SnCl ₂in the tetrahydrofuran solvent existing, be warming up to 100 ℃, reflux 10h, stopped reaction, makes described 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

5. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, in step (1), described alkali 1 is Bu ₃n, described alkali 1 is 1:1 with the mole dosage ratio of acetylene compound.

6. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, in step (1), described catalyzer 1 is Pd (OAc) ₂, the mole dosage of described catalyzer 1 is 10% of 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides.

7. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, in step (3), described catalyzer 2 is Pd (PPh ₃) ₄, the mole dosage of described catalyzer 2 is the 0.05%-20% of compound 3; In step (3), described alkali 2 is Na ₂cO ₃, the mole dosage of described alkali 2 is 2-20 times of compound 4.

8. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, described in step (1), solvent 1 is DMF; Described in step (2), solvent 2 is THF; Described in step (3), solvent 3 is tetrahydrofuran (THF), glycol dimethyl ether, benzene or toluene.

9. the also preparation method of [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer that contains according to claim 3, is characterized in that, described rare gas element is nitrogen or helium.

Described in claim 1 or 2 containing [3,2-b] two selenophens-benzo two (diazosulfide) multipolymer also at polymer solar battery, organic electroluminescent, organic field effect tube, the application in organic optical storage and organic laser field.

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