CN104072732B - Containing the multipolymer and its preparation method and application of di-selenophen-benzo two (selenole) - Google Patents

Abstract

The invention provides a kind of multipolymer containing di-selenophen-benzo two (selenole), general structure is as follows: P: wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.The energy gap of the above-mentioned multipolymer containing di-selenophen-benzo two (selenole) is narrower.The present invention also provides the preparation method of the above-mentioned multipolymer containing di-selenophen-benzo two (selenole), using should containing the organic solar batteries device of the multipolymer of di-selenophen-benzo two (selenole) and organic electroluminescence device.

Description

Containing the multipolymer and its preparation method and application of di-selenophen-benzo two (selenole)

Technical field

The present invention relates to photoelectric field, particularly relate to a kind of multipolymer containing di-selenophen-benzo two (selenole) and its preparation method and application.

Background technology

The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point of photovoltaic art always.Business-like silicon solar cell is high due to complex manufacturing, cost at present, makes it apply and is restricted.In order to reduce costs, expansive approach scope, 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 low in raw material price, quality are light, flexibility, simple, the available coating of production technique, printing such as to prepare at the advantage.Above conjugated polymers and C is reported at SCIENCE (N.SSariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) from N.S.Sariciftci in 1992 etc. ₆₀between Photo-induced electron transfer phenomenon after, people have dropped into large quantity research in polymer solar battery, and achieve development at full speed.

But the band gap of traditional polymkeric substance (energy level difference between HOMO energy level and lumo energy) is wider, absorption spectrum can not mate well with solar spectrum, reduce the specific absorption to photon in solar spectral, thus make to use the effciency of energy transfer of the organic solar batteries of traditional polymkeric substance lower.

Summary of the invention

Based on this, be necessary multipolymer containing di-selenophen-benzo two (selenole) providing a kind of band gap narrower and preparation method thereof.

In addition, there is a need to provide a kind of and use organic solar batteries device and the organic electroluminescence device that should contain the multipolymer of di-selenophen-benzo two (selenole).

A kind of multipolymer containing di-selenophen-benzo two (selenole), general structure is as follows:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

A kind of preparation method of the multipolymer containing di-selenophen-benzo two (selenole), comprises the steps:

The compd A and compd B with following structural formula are provided:

A is: b is: wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere; be that described compd A and the described compd B of 1:1.5 ~ 1.5:1 carries out Stille coupling reaction in the organic solvent containing organic palladium catalyzer by mol ratio, after separating-purifying, obtain the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

Wherein in an embodiment, described organic palladium catalyzer is selected from three (dibenzalacetone) two palladium, tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, and the mol ratio of described organic palladium catalyzer and described compd A is 1:2000 ~ 1:5.

Wherein in an embodiment, the temperature of reaction of described Stille coupling reaction is 50 DEG C ~ 120 DEG C, and the reaction times is 6 hours ~ 100 hours.

Wherein in an embodiment, described separating-purifying is as follows containing the step of the copolymer p of di-selenophen-benzo two (selenole): the mixed solution adding toluene and deionized water in the solution after Stille coupling reaction carries out extraction and retains organic phase, add precipitating in ethanol after removing at least part of organic solvent and filter, dissolve after the pressed powder drying obtained after filtration with chloroform, use neutral alumina chromatography, remove organic solvent afterwards, again filter by methyl alcohol precipitating, by the solids acetone extraction obtained after filtration, to collect after acetone soln by methyl alcohol precipitating and filter.

Wherein in an embodiment, described compd A is obtained by following steps:

Compound C, n-Butyl Lithium and tributyltin chloride are provided,

The structural formula of Compound C is wherein R ₃, R ₄for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere, described Compound C is added in tetrahydrofuran (THF), n-Butyl Lithium is added at-78 DEG C, the mol ratio of described Compound C and described n-Butyl Lithium is 1:2, stirring reaction 1 hour ~ 2 hours, tributyltin chloride is added at-78 DEG C, the mol ratio of described tributyltin chloride and described Compound C is 2:1, react 1 hour at-78 DEG C, be warming up to stirring at room temperature and react 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by suction filtration after the organic phase drying that obtains, solvent in removing filtrate, neutral alumina column chromatography is used to obtain described compd A.

Wherein in an embodiment, described compd B is obtained by following steps:

The Compound D and compd E with following structural formula are provided:

D is: e is: wherein R ₁, R ₂for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere; be that described Compound D and the described compd E of 1:2 carries out ring closure reaction in the organic solvent containing organic bases and catalyzer by mol ratio; obtain described compd B after separating-purifying, described organic bases is tributylamine, and described catalyzer is palladium.

Wherein in an embodiment, the step of described separating-purifying compd B is as follows: the reaction solution after described Compound D and compd E are carried out ring closure reaction uses water and dichloromethane extraction successively, retain organic layer, anhydrous sodium sulfate drying, filter, distillation obtains described compd B except using silica gel column chromatography to be separated after desolventizing.

A kind of organic solar batteries device, comprises active coating, and the material of described active coating comprises the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

A kind of organic electroluminescence device, comprises luminescent layer, and the material of described luminescent layer is the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

Above-mentioned multipolymer containing di-selenophen-benzo two (selenole) and preparation method thereof, synthetic method is simple; Improve solvability containing the multipolymer of di-selenophen-benzo two (selenole) and molecular weight by introducing alkyl, being conducive to film forming processing; Benzo two (selenole) has two dimensional structure, structure is simple, symmetrical, and the selenium atom atomic radius in benzo two (selenole) is larger, the molecule that can strengthen between polymer chain is overlapping, promote the transfer of electric charge, there is good electron transport ability, it is a kind of very excellent acceptor material, multipolymer containing di-selenophen-benzo two (selenole) can form a kind of very strong donor-receiver structure, be conducive to the stability that improve material on the one hand, be conducive to the band gap reducing material on the other hand; The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) is applied to solar cell and can increases substantially effciency of energy transfer; The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) is applied to organic electroluminescence device and can increases substantially luminous efficiency.

Accompanying drawing explanation

Fig. 1 is the schema of the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) of an embodiment;

Fig. 2 is the structural representation of the organic solar batteries device of an embodiment;

Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment.

Embodiment

For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.

The multipolymer containing di-selenophen-benzo two (selenole) of one embodiment, general structure is as follows:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100, and preferred n is the integer of 19 ~ 50.

The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) improves solvability containing the multipolymer of di-selenophen-benzo two (selenole) and molecular weight by introducing alkyl, is conducive to film forming and processes; Benzo two (selenole) has two dimensional structure, structure is simple, symmetrical, and the selenium atom atomic radius in benzo two (selenole) is larger, the molecule that can strengthen between copolymer chain is overlapping, promote Charger transfer, there is good electron transport ability, it is a kind of very excellent acceptor material, multipolymer containing di-selenophen-benzo two (selenole) can form a kind of very strong donor-receiver structure, be conducive to the stability that improve material on the one hand, be conducive to the band gap reducing material on the other hand.

As shown in Figure 1, the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) of an embodiment, comprises the steps:

Step S100, provide compd A and compd B.

Compd A and compd B have following structural formula respectively:

A is: b is: wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl.

The preparation of compd A comprises the following steps:

Step S111, provide Compound C, n-Butyl Lithium and tributyltin chloride.

The structural formula of Compound C is wherein R ₃, R ₄for C ₁~ C ₂₀alkyl.

Step S112, under protective gas atmosphere, Compound C to be added in tetrahydrofuran (THF), at-78 DEG C, add n-Butyl Lithium (CH ₃(CH ₂) ₃li), stirring reaction 1 hour ~ 2 hours, adds tributyltin chloride (SnBu at-78 DEG C ₃cl), react 1 hour at-78 DEG C, be warming up to stirring at room temperature and react 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by suction filtration after the organic phase drying that obtains, the solvent in removing filtrate, uses neutral alumina column chromatography to obtain compd A.

Preferably, protective gas is selected from least one in nitrogen and argon gas.

Preferably, neutral alumina column chromatography is used to purify the compd A obtained.

Preferably, the mol ratio of Compound C and n-Butyl Lithium is 1:2.

Preferably, the mol ratio of tributyltin chloride and Compound C is 2:1.

Preferably, the solid-to-liquid ratio of Compound C and saturated sodium-chloride water solution is 1mol:3L.

The preparation of compd B comprises the following steps:

Step S121,2-amino-5-N-methyl-p-nitroaniline is added thionyl chloride (SOCl ₂) in, (structural formula is to drip pyridine while stirring molecular formula is C ₅h ₅n), wherein the solid-to-liquid ratio of 2-amino-5-N-methyl-p-nitroaniline and pyridine is 3mol:40mL, be heated to 80 DEG C ~ 90 DEG C back flow reaction 24 hours afterwards, remove excessive thionyl chloride afterwards, precipitating in deionized water is added after cooling, collect the drying of solids wash final vacuum after filtration washing and obtain 5-nitro-2,1,3 diazosulfide.

The reaction formula of this step is:

Step S122, by 5-nitro-2,1,3 diazosulfide and hydrobromic acid solution mixing after at 127 DEG C reflux, to 5-nitro-2,1,3 diazosulfide and Hydrogen bromide (HBr) solution mixing after formed mixed solution in drip bromine (Br ₂), back flow reaction 4 hours, heat filtering afterwards, refilters after filtrate being cooled, dry after the solids washed with water obtained, then obtains 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide with Glacial acetic acid and Gossypol recrystallized from chloroform successively.

The reaction formula of this step is:

Preferably, in hydrobromic acid solution, hydrobromic mass percentage is 40%.5-nitro-2,1,3 diazosulfide and mass percentage are the solid-to-liquid ratio of the hydrobromic acid solution of 40% is 4mmol:1mL.

Preferably, the solid-to-liquid ratio of 5-nitro-2,1,3 diazosulfide and bromine is 60mmol:11.3mL.

Step S123, be 4 of 102:95 by mass ratio, the bromo-5-nitro-2 of 7-bis-, 1,3 diazosulfides and copper powder (Cu) add N, in dinethylformamide (DMF), react 3 hours at 120 DEG C, add toluene agitation and filtration after being cooled by reaction solution, by filtrate with the aqueous solution of saturated sodium-chlor and water washing, merge organic phase, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtain 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfides.

The reaction formula of this step is:

Preferably, the solid-to-liquid ratio of 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide and DMF is 1mol:3L.The volume ratio of DMF and toluene is 1:1.

Step S114, be 4 of 1:10,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1 by mol ratio, 3 diazosulfides and SnCl ₂add in tetrahydrofuran (THF) (THF), be warming up to 100 DEG C, back flow reaction 10 hours, use sodium hydroxide solution that the pH value of reaction solution is adjusted to 8 after cooling, use anhydrous diethyl ether extraction afterwards, collection organic phase also removing organic solvent wherein obtains solid crude product, after solid crude product and mixed in hydrochloric acid, drip sodium nitrite solution, react 30 minutes below 5 DEG C, reaction solution is added dropwise in liquor kalii iodide, vigorous stirring reacts 12 hours, then with sodium hydroxide solution, the pH value of reaction solution is adjusted to 7, extract with anhydrous diethyl ether, collect organic phase after washing, filter, the organic solvent removed in filtrate obtains 4 afterwards, 4 '-two bromo-6, 6 '-two iodo-2, 1, 3 diazosulfides.

The reaction formula of this step is:

Preferably, 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, in 3 diazosulfides and hydrochloric acid, the mol ratio of hydrogenchloride is 20:21.7.4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, the mol ratio of 3 diazosulfides and Sodium Nitrite is 20:37.7.4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1, the mass ratio of 3 diazosulfides and potassiumiodide is 10.3:62.

Preferably, 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfide silica gel column chromatographies are separated, then purify by recrystallizing methanol.

Preferably, in liquor kalii iodide, the solid-to-liquid ratio of potassiumiodide and water is 31g:50mL.

Step S125, by 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides add in ethanol and form suspension, instill in suspension at 0 DEG C by sodium borohydride, at room temperature stirring reaction 20 hours, with anhydrous diethyl ether extraction, collect organic phase after washing, filter, the organic solvent removed in filtrate obtains 4 afterwards, 4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine).

Preferably, 4,4 '-two bromo-6,6 '-two iodo-2, the mol ratio of 1,3 diazosulfides and sodium borohydride is 1:37.4,4 '-two bromo-6,6 '-two iodo-2, the solid-to-liquid ratio of 1,3 diazosulfides and ethanol is 6.8g:200mL.

The reaction formula of this step is:

Step S126,4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine) are added in ethanolic soln and reflux, drip SeO ₂after the aqueous solution, back flow reaction 2 hours, obtains 4 after filtration, and 4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles (Compound D).

Preferably, 4,4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine) and SeO ₂mol ratio be 5:10.5.4,4 '-two bromo-6, the solid-to-liquid ratio of 6 '-two iodo-di-(1,2-phenylenediamine) and ethanol is 3.12g:60mL.SeO ₂the concentration of the aqueous solution is 0.48mol/L.

The reaction formula of this step is:

Step S127, under protective gas atmosphere, be that Compound D and the compd E of 1:2 carries out ring closure reaction in the organic solvent containing organic bases and catalyzer by mol ratio, organic bases is tributylamine (Bu ₃n), catalyzer is palladium (Pd (OAc) ₂), obtain compd B after separating-purifying.

The structural formula of Compound D and compd E is as follows:

D is: e is: wherein R ₁, R ₂for C ₁~ C ₂₀alkyl.

The reaction formula of this step is:

Preferably, protective gas is selected from least one in nitrogen and argon gas.

Preferably, solvent is DMF (DMF).

Preferably, the mol ratio of organic bases and compd E is 1:1.

Preferably, the mol ratio of Compound D and catalyzer is 10:1.

Preferably, temperature of reaction is 130 DEG C, and the reaction times is 4 hours.

Preferably, the step of separating-purifying compd B is as follows: the reaction solution after Compound D and compd E are carried out ring closure reaction uses water and dichloromethane extraction successively, retains organic layer, anhydrous sodium sulfate drying, filter, distillation obtains compd B except using silica gel column chromatography to be separated after desolventizing.

Step S200, under protective gas atmosphere; be that compd A and the compd B of 1:1.5 ~ 1.5:1 carries out Stille coupling reaction in the organic solvent containing organic palladium catalyzer by mol ratio, after separating-purifying, obtain the copolymer p containing di-selenophen-benzo two (selenole).

Copolymer p containing di-selenophen-benzo two (selenole) has following structural formula:

P is: wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

In present embodiment, protective gas is selected from least one in nitrogen and argon gas.

In present embodiment, organic palladium catalyzer is selected from three (dibenzalacetone) two palladium (Pd ₂(dba) ₃), tetrakis triphenylphosphine palladium (Pd (PPh ₃) ₄) or two (triphenylphosphine) palladium chloride (Pd (PPh ₃) ₂cl ₂) at least one, be preferably Pd (PPh ₃) ₂cl ₂.Be appreciated that organic palladium catalyzer is not limited to cited kind, as long as energy catalytic cpd A and compd B carry out Stille coupling reaction.

In present embodiment, organic solvent is selected from tetrahydrofuran (THF) (THF), glycol dimethyl ether (DME), benzene (C ₆h ₆) and toluene (C ₇h ₈) at least one.Be appreciated that organic solution also can use other solvents, as long as can dissolved compound A and compd B.

In present embodiment, the mol ratio of organic palladium catalyzer and compd A is 1:2000 ~ 1:5.Be appreciated that the mol ratio of organic palladium catalyzer and compd A is not limited to 1:2000 ~ 1:5, in the organic solvent adding compd A and compd B, add the catalyzer of catalytic amount.

In present embodiment, the temperature of reaction of Stille coupling reaction is 50 DEG C ~ 120 DEG C, and the reaction times is 6 hours ~ 100 hours.Compd A and compd B be appreciated that the temperature of reaction of Stille coupling reaction is not limited to 50 DEG C ~ 120 DEG C, as long as can be made to react; Reaction times is also not limited to 6 hours ~ 100 hours, as long as compd A and compd B can be made to react completely as far as possible.

In present embodiment, separating-purifying is as follows containing the step of the multipolymer of di-selenophen-benzo two (selenole): the mixed solution adding toluene and deionized water in the solution after carrying out Stille coupling reaction to compd A and compd B carries out extraction and retains organic phase, add precipitating in ethanol after removing at least part of organic solvent and filter, dissolve after the pressed powder drying obtained after filtration with chloroform, use neutral alumina chromatography, remove organic solvent afterwards, again filter by methyl alcohol precipitating, by the solids acetone extraction obtained after filtration, also filter the multipolymer containing di-selenophen-benzo two (selenole) obtaining purifying by methyl alcohol precipitating after collecting acetone soln.

The preparation method of the above-mentioned multipolymer containing di-selenophen-benzo two (selenole), synthetic method is simple.

It should be noted that, each step of above-mentioned reaction is not limited to adopt said sequence to perform, and each step such as preparing compd B can perform prior to each step preparing compd A, also can perform with each step preparing compd A simultaneously.

The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) has lower band gap.The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) is applied to solar cell and can increases substantially effciency of energy transfer.The above-mentioned multipolymer containing di-selenophen-benzo two (selenole) is applied to organic electroluminescence device and can increases substantially luminous efficiency.This multipolymer containing di-selenophen-benzo two (selenole) can also be applied to the fields such as organic field effect tube, organic optical storage, organic non-linear optical properties and organic laser.

Be specific embodiment below.

Embodiment 1

Present embodiment discloses structural formula following poly-{ 4,4 '-dioctyl-2,2 '-di-selenophen-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } (copolymer p 1 containing di-selenophen-benzo two (selenole)):

wherein, n=50.

The preparation process of the above-mentioned copolymer p 1 containing di-selenophen-benzo two (selenole) is as follows:

Step one, preparation 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles

1.1, compound 5-nitro-2,1,3 diazosulfide is prepared

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

1.2, compound 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide is prepared

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

1.3,4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1 is prepared, 3 diazosulfides

The bromo-5-nitro-2,1 of 4,7-bis-is added in there-necked flask, 3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF (DMF) of 90mL, was heated to 120 DEG C of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90mL toluene, stir 30 minutes, filter, filtrate saturated sodium-chloride water solution and water washing, merge organic layer, anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate 30.2%.

1.4,4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides are prepared

In there-necked flask, add 4,4 '-two bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide (10.3g, 20mmol), adds the tetrahydrofuran (THF) (THF) of 300mL drying, adds 40gSnCl ₂(200mmol), 100 DEG C are warming up to, reflux 10h, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extracts, and revolves and steams gained organic layer, obtain 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 controls below 5 DEG C, solution, in yellow, after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide+100mL water), vigorous stirring, reaction 12h.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer is washed, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, be separated with silica gel column chromatography, then carry out recrystallizing methanol, obtain 4.1g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, productive rate is 30%.

1.5,4,4 '-two bromo-6 is prepared, 6 '-two iodo-di-(1,2-phenylenediamine)

In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides (6.80g, 0.01mol), add the ethanol of 200mL, form suspension, 0 DEG C drips sodium borohydride (14g, 0.37mol), mixture stirring reaction 20 hours under room temperature, stopped reaction, extracts with anhydrous diethyl ether, organic layer is washed, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, obtain 5.49g product, productive rate 88%.

1.6,4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles are prepared

In there-necked flask, add 4,4 '-two bromo-6,6 '-two iodo-di-(1,2-phenylenediamine) (3.12g, 5mmol), adds the ethanolic soln of 60mL, backflow, drips SeO ₂(1.17g, 10.5mmol) aqueous solution (hot water 22mL), reaction mixture refluxed 2 hours, stopped reaction, filters, obtains 3.48g product, productive rate 90%.

Step 2, prepare bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3, the 4-e] two (selenole) of compound 4,9-bis-

4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 selenoles (3.87g, 5mmol), add 2,6,13,17-tetramethyl--9-octadecyne (3.07g, 10mmol) (synthetic method reference Chem.Commun., 2011,47,8850-8852), 25mLDMF, pass into nitrogen gas stirring 20min, add Bu ₃n (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, and obtains 2.48g product 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 60%.

Proton nmr spectra and the carbon-13 nmr spectra test result of 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenole) are as follows:

¹HNMR(CDCl ₃)δ(TMS，ppm)：7.25(d，2H)，2.57(dd，4H)，1.83(d，2H)，1.67(d，2H)，1.58(d，4H),1.25-1.30(m，12H),1.02-1.07(m,18H)；

¹³CNMR(CDCl ₃)δ(TMS，ppm)：160.0,138.7,133.8,133.0,126.3,104,41.0,39.7,38.0,32.6,28.5,24.4,23.0,21.0。

Step 3, preparation 4,4 '-dioctyl-5,5 '-two (tributyl tinbase)-2,2 '-di-selenophen

Under the protection of nitrogen, in there-necked flask, add 4,4 '-dioctyl-5; 5 '-two bromo-2; 2 '-di-selenophen (6.42g, 0.01mol), adds the tetrahydrofuran solvent of 70ml; n-Butyl Lithium (2.5M is slowly injected with syringe again under-78 DEG C of conditions; 0.02mol), continue stirring reaction 2h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), rise to stirred at ambient temperature and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, obtain organic layer, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productive rate 65%.

Step 4, preparation poly-{ 4,4 '-dioctyl-2,2 '-di-selenophen-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) }

Under nitrogen protection, add 4,4 '-dioctyl-5; 5 '-two (tributyl tinbase)-2,2 '-di-selenophen (212.6mg, 0.2mmol), 4; 9-bis-bromo-6; 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3; 4-e] two (selenole) (165.2mg; 0.2mmol) with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh ₃) ₂cl ₂(5mg, 7.1 × 10 ^-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.

Polymkeric substance (P1) after purifying is carried out GPC test, number-average molecular weight Mn ≈ 58950, n=50, and polymkeric substance monodispersity is 2.4.

Embodiment 2

Present embodiment discloses structural formula following poly-{ 4,4 '-dimethyl-2,2 '-di-selenophen-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenoles) } (copolymer p 2 containing di-selenophen-benzo two (selenole)):

wherein, n=20.

The preparation process of the above-mentioned copolymer p 2 containing di-selenophen-benzo two (selenole) is as follows:

Step one, preparation 4,4 '-dimethyl-5,5 '-two (tributyl tinbase)-2,2 '-di-selenophen

Under the protection of nitrogen, in there-necked flask, add 4,4 '-dimethyl-5; 5 '-two bromo-2; 2 '-di-selenophen (4.50g, 0.01mol), adds the tetrahydrofuran solvent of 50ml; n-Butyl Lithium (8.6mL is slowly injected with syringe again under-78 DEG C of conditions; 0.02mol), continue stirring reaction 1.5h, under-78 DEG C of conditions, inject tributyltin chloride (5.6mL with syringe; 0.02mol), react and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productive rate 62%.

Step 2, bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3, the 4-e] two (selenole) of preparation 4,9-bis-.

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

Step 3, poly-{ 4,4 '-dimethyl-2,2 '-di-selenophen-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) }

Under nitrogen protection, add 4,4 '-dimethyl-5; 5 '-two (tributyl tinbase)-2,2 '-di-selenophen (173.2mg, 0.2mmol), 4; 9-bis-bromo-6; 7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3; 4-e] two (selenole) (165.2mg; 0.2mmol) with tetrahydrofuran solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then adding Pd ₂(dba) (5mg, 5.5 × 10 ^-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.

Polymkeric substance (P2) after purifying is carried out GPC test, number-average molecular weight Mn ≈ 19660, n=20, and polymkeric substance monodispersity is 2.4.

Embodiment 3

Present embodiment discloses structural formula following poly-{ 4,4 '-two (NSC 62789 base)-2,2 '-di-selenophen-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenoles) } (copolymer p 3 containing di-selenophen-benzo two (selenole)):

wherein, n=19.

The preparation process of the above-mentioned copolymer p 3 containing di-selenophen-benzo two (selenole) is as follows:

Step one, preparation 4,4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles.

4,4 '-two bromo-6,6 '-two iodo-2, the preparation of 1,3 selenoles is with the step one of embodiment 1.

Step 2, preparation 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole)

4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 selenoles (7.74g, 10mmol), add valerylene (1.36g, 20mmol) (synthetic method reference Chem.Commun., 2011,47,8850-8852), 50mLDMF, passes into nitrogen gas stirring 20min, adds Bu ₃n (1.814g, 20mmol) and Pd (OAc) ₂(230mg, 1.0mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, obtain 5.15g product 4,9-bis-bromo-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productive rate 65%.

Proton nmr spectra and the carbon-13 nmr spectra test result of 4,9-bis-bromo-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (selenole) are as follows:

¹HNMR(CDCl ₃)δ(TMS，ppm)：7.25(d，2H)，2.57(dd，4H)，2.30(d，2H)，1.24(d，3H)；

¹³CNMR(CDCl ₃)δ(TMS，ppm)：160.0,138.7,133.8,133.0,126.3,104,41.0,15.3，12.4。

Step 3, preparation 4,4 '-two (NSC 62789 base)-5,5 '-two (tributyl tinbase)-2,2 '-di-selenophen

Under the protection of nitrogen; 4 are added in there-necked flask; 4 '-two (NSC 62789 base)-5; 5 '-two bromo-2; 2 '-di-selenophen (9.79g; 0.01mol); add the tetrahydrofuran solvent of 100ml; n-Butyl Lithium (8.6mL, 2.5M, 0.02mol) is slowly injected with syringe again under-78 DEG C of conditions; continue stirring reaction 1h; under-78 DEG C of conditions, inject tributyltin chloride (5.6mL, 0.02mol) with syringe, react and be warming up to stirred at ambient temperature after 1 hour and react 6 hours.Add saturated sodium-chloride water solution (30ml) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering, filtrate collection is revolved and evaporates solvent.Finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productive rate 74%.

Step 4, preparation poly-{ 4,4 '-two (NSC 62789 base)-2,2 '-di-selenophen-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }

Under nitrogen protection; add 4,4 '-two (NSC 62789 base)-5,5 '-two (tributyl tinbase)-2; 2 '-di-selenophen (279.8mg; 0.2mmol), 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3; 4-e] two (selenole) (117.6mg; 0.2mmol) with toluene solvant 40ml, vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh ₃) ₄(9mg, 7.8 × 10 ^-3mmol), 90 DEG C of reaction 72h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.

Polymkeric substance (P3) after purifying is carried out GPC test, number-average molecular weight Mn ≈ 24263, n=19, and polymkeric substance monodispersity is 2.5.

Embodiment 4

Present embodiment discloses structural formula following poly-{ 4,4 '-two (NSC 62789 base)-2,2 '-di-selenophen-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenoles) } (copolymer p 4 containing di-selenophen-benzo two (selenole)):

wherein, n=100.

The preparation process of the above-mentioned copolymer p 4 containing di-selenophen-benzo two (selenole) is as follows:

Step one, preparation 4,4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles.

4,4 '-two bromo-6,6 '-two iodo-2, the preparation of 1,3 selenoles is with the step one of embodiment 1.

Step 2, preparation 4,9-bis-bromo-6-(2,7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfide)

4 are added, 4 '-two bromo-6,6 '-two iodo-2 in there-necked flask, 1,3 selenoles (3.87g, 5mmol), (synthetic method is with reference to Chem.Commun. to add 2,6-dimethyl-9-30 alkynes (4.47g, 10mmol), 2011,47,8850-8852), 30mLDMF, pass into nitrogen gas stirring 20min, add Bu ₃n (0.907g, 10mmol) and Pd (OAc) ₂(115mg, 0.5mmol), is warming up to 130 DEG C, heating 4h, cooling, washing, dichloromethane extraction, obtain organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography is separated, and obtains 2.7g product 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productive rate 62%.

Proton nmr spectra and the carbon-13 nmr spectra test result of 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenole) are as follows:

¹HNMR(CDCl ₃)δ(TMS，ppm)：7.25(d，2H)，2.57(dd，4H)，1.83(d，1H)，1.65(d，3H)，1.59(d，2H),1.25-1.32(m，40H),0.98-1.03(m,12H)；

¹³CNMR(CDCl ₃)δ(TMS，ppm)：160.0,138.7,133.8,133.0,126.3,104,41.0,39.7,38.0,32.6,32.0，31.7，29.7，29.1，28.5,24.4,24.0,23.0，22.6，21.6，21.0，14.0。

Step 3, preparation 4,4 '-two (NSC 62789 base)-5,5 '-two (tributyl tinbase)-2,2 '-di-selenophen.

The preparation of 4,4 '-two (NSC 62789 base)-5,5 '-two (tributyl tinbase)-2,2 '-di-selenophen is with the step 3 of embodiment 3.

Step 4, preparation poly-{ 4,4 '-two (NSC 62789 base)-2,2 '-di-selenophen-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenole) }

Under nitrogen protection, add 4,4 '-two (NSC 62789 base)-5; 5 '-two (tributyl tinbase)-2; 2 '-di-selenophen (419.7mg, 0.3mmol), 4,9-bis-bromo-6-(2; 7-dimethyl) octyl group-7-eicosyl benzo [2; 1-e:3,4-e] two (selenole) (193.4mg, 0.2mmol) and glycol dinitrate ether solvents 40ml; vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh ₃) ₂cl ₂(28.04mg, 0.04mmol), is heated to 120 DEG C of reaction 100h.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.

Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 165600, n=100, and polymkeric substance monodispersity is 6.2.

Embodiment 5

Present embodiment discloses structural formula following poly-{ 4,4 '-dimethyl-2,2 '-di-selenophen-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) } (copolymer p 5 containing di-selenophen-benzo two (selenole)):

wherein n=1.

The preparation process of the above-mentioned copolymer p 5 containing di-selenophen-benzo two (selenole) is as follows:

Step one, preparation 4,4 '-dimethyl-5,5 '-two (tributyl tinbase)-2,2 '-di-thiophene.

4,4 '-dimethyl-5, the preparation of 5 '-two (tributyl tinbase)-2,2 '-di-thiophene is with the step one of embodiment 2.

Step 2, preparation 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole).

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

Step 3, preparation poly-{ 4,4 '-dimethyl-2,2 '-di-selenophen-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }

Under nitrogen protection; add 4,4 '-dimethyl-5,5 '-two (tributyl tinbase)-2; 2 '-di-selenophen (173.2mg; 0.2mmol), 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3; 4-e] two (selenole) (176.4mg; 0.3mmol) with benzene solvent 40ml, vacuumize deoxygenation and be filled with nitrogen, then adding Pd (PPh ₃) ₂cl ₂(1.05mg, 1.5 × 10 ^-4mmol) 50 DEG C of reaction 6h are heated to.After reaction, deionized water is added and toluene extracts in the reaction flask of product, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about about 5ml, be added dropwise in 400ml dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Again pressed powder chloroform is dissolved, cross chromatography column with neutral alumina, decompression removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.

Polymkeric substance after purifying is carried out GPC test, number-average molecular weight Mn ≈ 744, n=1.

Embodiment 6

Refer to Fig. 2, the organic solar batteries device 40 of an embodiment comprises the substrate 41, anode 42, middle supplementary layer 43, active coating 44 and the negative electrode 45 that stack gradually.

In the present embodiment, substrate 41 is glass.

Anode 42 is formed at a side surface of substrate 41.In the present embodiment, anode 42 is ITO (tin indium oxide), preferably, and the tin indium oxide of ITO to be square resistance be 10 Ω/.In present embodiment, the thickness sum of substrate 41 and anode 42 is 1.1mm.Preferably, substrate 41, before formation anode 42, first cleans, and oxygen plasma treatment.

Middle supplementary layer 43 is formed at the surface of anode 42.The material of middle supplementary layer 43 comprises poly-(3,4-ethylenedioxy di-thiophene) and polystyrolsulfon acid (PEDOT:PSS, both ": " expressions mixing) (CLEVIOSPVPAl4083).The thickness of middle supplementary layer 43 is 120nm.Middle supplementary layer 43 is prepared by spin coating.

Active coating 44 is formed at the surface of middle supplementary layer 43.The material of active coating 44 comprises the methyl-butyrate derivative (PCBM) of soccerballene and has the copolymer p containing di-selenophen-benzo two (selenole) of following structural formula:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

Be wherein 5:4 containing the copolymer p of di-selenophen-benzo two (selenole) and the mass ratio of PCBM.The thickness of active coating 44 is 150nm.When preparing active coating 44, after 10mg is dissolved in 0.4mL dimethylbenzene containing the copolymer p of di-selenophen-benzo two (selenole), is spun on drying on middle supplementary layer 43 after the solution blending that the chlorobenzene being dissolved in 0.4mL is formed obtains with 8mgPCBM.

Negative electrode 45 is formed at the surface of active coating 44.The material of negative electrode 45 is aluminium (Al).The thickness of negative electrode 45 is 110nm.Negative electrode 45 is prepared by vacuum evaporation, and vacuum tightness is 2 × 10 ^-3pa.

Above-mentioned all preparation process are all carried out in the glove box providing nitrogen inert atmosphere.

It should be noted that, substrate 41, anode 42, middle supplementary layer 43 and negative electrode 45 material used is not limited to above cited material, also can be other materials conventional in the industry, also can arrange other functional layers as required.

Respectively the copolymer p 1 ~ P3 containing di-selenophen-benzo two (selenole) prepared by embodiment 1 ~ 3 is applied to organic solar batteries device 40, by Keithley236 current/voltage source-measuring system and a calibrated silicon photo diode test current-voltage characteristic under AM1.5G, result is as shown in the table.

From upper table data, the energy conversion efficiency of the organic solar batteries device prepared as active coating with multipolymer of the present invention is 0.95 ~ 1.34, show that the multipolymer containing di-selenophen-benzo two (selenole) of the present invention is due to containing new benzo two (selenole) conjugate unit, high with the matching degree of solar spectrum, it is planar conjugate structure simultaneously, carrier mobility speed is high, ratio and charge collection efficiency that current carrier arrives electrode can be improved, thus raising effciency of energy transfer, and the improvement passed through device architecture or modification, higher effciency of energy transfer can be obtained.

Embodiment 7

Refer to Fig. 3, a kind of organic electroluminescence device 70 comprises the substrate 71, anode 72, the anode buffer layer 73 that stack gradually, luminescent layer 74, cathode buffer layer 75 and negative electrode 76.

In the present embodiment, substrate 71 is glass.

Anode 72 is formed at a side surface of substrate 71.In the present embodiment, anode 72 is ITO (tin indium oxide), preferably, and the tin indium oxide of ITO to be square resistance be 10 Ω/.The thickness of anode 72 is 150nm.

Anode buffer layer 73 is formed at the surface of anode 72.The material of anode buffer layer 74 is the mixture (CLEVIOSPVPAl4083) of poly-3,4-dioxyethylene thiophene (PEDOT) and polyphenyl sulfonate (PSS).The thickness of anode buffer layer 73 is 30nm.

Luminescent layer 74 is formed at the surface of anode buffer layer 73.The material of luminescent layer 74 is the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

Specifically in the present embodiment, the material of luminescent layer 74 is the copolymer p 1 containing di-selenophen-benzo two (selenole) prepared by embodiment 1.

The thickness of luminescent layer 74 is 90nm.

Cathode buffer layer 75 is formed at the surface of luminescent layer 74.The material of cathode buffer layer 75 is lithium fluoride (LiF).The thickness of cathode buffer layer 75 is 1.5nm.Cathode buffer layer 75 is formed by evaporation.

Negative electrode 76 is formed at the surface of cathode buffer layer 75.The material of negative electrode is aluminium (Al).The thickness of negative electrode 76 is 150nm.

It should be noted that, substrate 71, anode 72, anode buffer layer 73, cathode buffer layer 75 and negative electrode 76 material used is not limited to above cited material, also can be other materials conventional in the industry, also can arrange other functional layers as required.

By organic electroluminescence device 70 by Keithley source measuring system (Keithley2400Sourcemeter) test current-brightness-voltage characteristic, by spectrograph (French JY company SPEXCCD3000) testing electroluminescent spectrum, all tests all complete in atmosphere at room temperature.The high-high brightness efficiency that test obtains organic electroluminescence device 70 is 12.8cd/A, and high-high brightness is 1168cd/m ².

The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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., containing a multipolymer for di-selenophen-benzo two (selenole), it is characterized in that, general structure is as follows:

P:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

2., containing a preparation method for the multipolymer of di-selenophen-benzo two (selenole), it is characterized in that, comprise the steps:

The compd A and compd B with following structural formula are provided:

A is: b is: wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere; be that described compd A and the described compd B of 1:1.5 ~ 1.5:1 carries out Stille coupling reaction in the organic solvent containing organic palladium catalyzer by mol ratio, after separating-purifying, obtain the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

P:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

3. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 2, it is characterized in that, described organic palladium catalyzer is selected from three (dibenzalacetone) two palladium, tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, and the mol ratio of described organic palladium catalyzer and described compd A is 1:2000 ~ 1:5.

4. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 2, it is characterized in that, the temperature of reaction of described Stille coupling reaction is 50 DEG C ~ 120 DEG C, and the reaction times is 6 hours ~ 100 hours.

5. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 2, it is characterized in that, described separating-purifying is as follows containing the step of the copolymer p of di-selenophen-benzo two (selenole): the mixed solution adding toluene and deionized water in the solution after Stille coupling reaction carries out extraction and retains organic phase, add precipitating in ethanol after removing at least part of organic solvent and filter, dissolve after the pressed powder drying obtained after filtration with chloroform, use neutral alumina chromatography, remove organic solvent afterwards, again filter by methyl alcohol precipitating, by the solids acetone extraction obtained after filtration, to collect after acetone soln by methyl alcohol precipitating and filter.

6. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 2, it is characterized in that, described compd A is obtained by following steps:

Compound C, n-Butyl Lithium and tributyltin chloride are provided,

The structural formula of Compound C is wherein R ₃, R ₄for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere, described Compound C is added in tetrahydrofuran (THF), n-Butyl Lithium is added at-78 DEG C, the mol ratio of described Compound C and described n-Butyl Lithium is 1:2, stirring reaction 1 hour ~ 2 hours, tributyltin chloride is added at-78 DEG C, the mol ratio of described tributyltin chloride and described Compound C is 2:1, react 1 hour at-78 DEG C, be warming up to stirring at room temperature and react 6 hours, add the aqueous solution termination reaction of saturated sodium-chlor, with anhydrous diethyl ether extractive reaction liquid, by suction filtration after the organic phase drying that obtains, solvent in removing filtrate, neutral alumina column chromatography is used to obtain described compd A.

7. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 2, it is characterized in that, described compd B is obtained by following steps:

The Compound D and compd E with following structural formula are provided:

D is: e is: wherein R ₁, R ₂for C ₁~ C ₂₀alkyl;

Under protective gas atmosphere; be that described Compound D and the described compd E of 1:2 carries out ring closure reaction in the organic solvent containing organic bases and catalyzer by mol ratio; obtain described compd B after separating-purifying, described organic bases is tributylamine, and described catalyzer is palladium.

8. the preparation method of the multipolymer containing di-selenophen-benzo two (selenole) according to claim 7, it is characterized in that, the step of described separating-purifying compd B is as follows: the reaction solution after described Compound D and compd E are carried out ring closure reaction uses water and dichloromethane extraction successively, retain organic layer, anhydrous sodium sulfate drying, filter, distillation obtains described compd B except using silica gel column chromatography to be separated after desolventizing.

9. an organic solar batteries device, comprises active coating, it is characterized in that, the material of described active coating comprises the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

P:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.

10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, the material of described luminescent layer is the copolymer p containing di-selenophen-benzo two (selenole) with following structural formula:

P:

Wherein, R ₁, R ₂, R ₃and R ₄for C ₁~ C ₂₀alkyl; N is the integer of 1 ~ 100.