CN102190680B - Silicon-containing thiophene organic photoelectric material and preparation method and application thereof - Google Patents
Silicon-containing thiophene organic photoelectric material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of organic materials, and provides a silicon-containing thiophene organic photoelectric material, which comprises compounds shown as a structural formula (1). In the formula, R1, R2, R3 and R4 are same or different, and refer to H or C1-C20 alkyl; and m and n are same or different and refer to an integer from 0 to 10. The invention also provides a manufacturing method for the silicon-containing thiophene organic photoelectric material and application of the silicon-containing thiophene organic photoelectric material. The silicon-containing thiophene organic photoelectric material has thiophene ring and cyan, so the silicon-containing thiophene organic photoelectric material has wider spectral response and higher thermal stability and environmental stability. The manufacturing method for the condensed ring thiophene organic photoelectric material has the advantages of simple synthetic route, low manufacturing cost and wide application prospect.
Description
Technical field
The invention belongs to organic materials technical field, be specifically related to a kind of siliceous thiophene organic photoelectrical material, its manufacture method and application thereof.
Background technology
Current world economy is to be mainly based upon with fossil energy, as the economy on the basis such as coal, oil and natural gas.But these non-renewable fossil energies are all in continuous exhaustion.Since entering 21 century, the problems such as global energy problem and consequent environmental pollution and climate warming show especially and aggravation gradually day by day.Distribute generally and wide because sun power has, resource quantity is many, pollution-free, clean, and safety and obtain the outstanding advantages such as convenient is considered to one of most promising renewable energy source.Solar cell directly changes into electric energy solar energy, is to utilize the practicable effective ways of sun power.But current commercial solar cell is also confined to the inorganic solar cell such as silica-based, but their price is too expensive, has exceeded the general acceptable degree of current people, and this has limited their use range greatly.In order to reduce battery cost, expand range of application, for a long time, people are finding novel solar cell material always.
Organic solar batteries is a kind of novel solar cell, for, complicated process of preparation limited, expensive, poisonous with respect to inorganic semiconductor material source, cost are too high, it has some incomparable advantages of inorganic solar cell, as material source extensively, structure diversity and Modulatory character, with low cost, safety and environmental protection, manufacture craft is simple, product weight is light, can prepare etc. by large area flexible, can be widely used in the multiple fields such as building, illumination and generating, there is important development and application prospect.Therefore, research institution and the enterprise etc. of lot of domestic and foreign have all given suitable concern and input.But up to the present, the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.Therefore, the organic photoelectrical material of development of new is significant for the efficiency that improves organic solar batteries and other semiconducter device.
Summary of the invention
In view of this, provide that a kind of spectral response is wide, the siliceous thiophene organic photoelectrical material of good stability, and the siliceous thiophene organic photoelectrical material manufacture method that a kind of synthetic route is simple, cost is low.
The embodiment of the present invention also provides above-mentioned siliceous thiophene organic photoelectrical material in the application of manufacturing in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus.
A kind of siliceous thiophene organic photoelectrical material, it comprises the compound that following structural formula (1) represents:
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical or different integers between 0-10 that is expressed as.
A kind of siliceous thiophene organic photoelectrical material manufacture method, it comprises the steps:
The compd A, B, C and the propane dinitrile that provide respectively following structural formula to represent,
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical or different integers between 0-10 that is expressed as, and An is C
1-C
4alkyl;
Under the condition of catalysts and solvents, compd A and B are carried out to condensation reaction or compd A and B and Compound C are carried out to Stille coupled reaction with propane dinitrile respectively;
Under the condition of catalysts and solvents, the product of condensation reaction and Compound C are carried out to Stille coupled reaction or the product of Stille coupled reaction and propane dinitrile are carried out to condensation reaction, obtain the compound that following structural formula (1) represents:
And above-mentioned siliceous thiophene organic photoelectrical material is in the application of manufacturing in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus.
In above-mentioned siliceous thiophene organic photoelectrical material, it has multiple thiphene ring structures, because thiphene ring is five-membered ring structure, meets shock youngster rule, has moderate band gap, wider spectral response, preferably thermostability and environmental stability.And owing to having two pairs of cyano group in above-mentioned siliceous thiophene organic photoelectrical material, cyano group is electron-withdrawing group, can further widen the spectral response range of material, and can improve the photoelectric properties of material.Further, the siliceous thiophene unit in material not only has above-mentioned similar effect, and two thiphene ring are in same plane, and this structure can effectively increase the conjugation performance of molecule, reduces the energy gap of material, expands the absorption region to sunlight.In above-mentioned siliceous thiophene organic photoelectrical material manufacture method, adopt better simply synthetic route, thereby reduce manufacturing cost.When above-mentioned siliceous thiophene organic photoelectrical material is applied in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus, can improve its photoelectricity or semi-conductor correlated performance, and can alleviate the quality of device, and be convenient to large batch of preparation.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the siliceous thiophene organic photoelectrical material manufacture method schema of the embodiment of the present invention;
Fig. 2 is the solar cell device structural representation that adopts the siliceous thiophene organic photoelectrical material of the embodiment of the present invention.
Fig. 3 is the structural representation that adopts the organic electroluminescence device of the siliceous thiophene organic photoelectrical material of the embodiment of the present invention.
Fig. 4 is the structural representation that adopts the organic field effect tube of the siliceous thiophene organic photoelectrical material of the embodiment of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of siliceous thiophene organic photoelectrical material compound, and it comprises the compound that following structural formula (1) represents:
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical or different integers between 0-10 that is expressed as.
In a preferred embodiment of the invention, siliceous thiophene organic photoelectrical material has symmetrical molecular structure, and m, n are the identical integer between 0-10, the i.e. m=n of being expressed as.In another embodiment of the present invention, m=n=0 or 1, now, and this siliceous thiophene organic photoelectrical material molecular weight, the quality product of making is lighter.In a preferred embodiment of the present invention, R
1and R
2for identical straight chained alkyl, be for example the straight chained alkyl with 6 carbon atoms, be hexyl.R
3, R
4for the identical C that is expressed as
8-C
18alkyl, be for example the alkyl with 8 carbon atoms, for example 2-ethyl-hexyl.
Above-mentioned siliceous thiophene organic photoelectrical material comprises multiple thiphene ring, has moderate band gap, wider spectral response, wave band is greatly about 300-700nm, substantially contain visible light wave range, also there is good thermostability and environmental stability, show good photoelectric properties.And, by introduce strong electron-withdrawing group group (as cyano group) in molecule 3-position, being conducive to form Electron donor acceptor between electron-donating group (as thiophene unit) interacts, make absorbing wavelength red shift, expand light abstraction width, improve the absorption rate to sunlight.Further, material has the siliceous thiophene unit of condensed ring, not only has above-mentioned similar effect, and two thiphene ring are in same plane, and this structure can effectively increase the conjugation performance of molecule, reduces the energy gap of material, expands the absorption region to sunlight.
In the siliceous thiophene organic photoelectrical material of the present embodiment, R
1, R
2, R
3, R
4be preferably alkyl chain, for example C
6or C
6above alkyl chain, by introducing alkyl chain to improve the solubility property of material, is conducive to film forming processing, expands its range of application.
Refer to Fig. 1, the manufacture method of above-mentioned siliceous thiophene organic photoelectrical material comprises the steps:
S10: the compd A, B, C and the propane dinitrile that provide respectively following structural formula to represent,
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical or different integers between 0-10 that is expressed as, and An is C
1-C
4alkyl;
S20: under the condition of catalysts and solvents, compd A and B are carried out to condensation reaction or compd A and B and Compound C are carried out to Stille coupled reaction with propane dinitrile respectively;
S30: under the condition of catalysts and solvents, the product of condensation reaction and Compound C are carried out to Stille coupled reaction or the product of Stille coupled reaction and propane dinitrile are carried out to condensation reaction, obtain the compound that following structural formula (1) represents:
In step S10, compd A, B, C and propane dinitrile can directly be buied from the market or prepare by existing synthetic method, are not described in detail in this.Wherein, the each group in compound A, B, C, with basic identical to the description of siliceous thiophene organic photoelectrical material above, does not repeat them here.
In step S20 and S30, the order of successively carrying out with Stille coupled reaction according to condensation reaction is different, can be divided into two kinds of possibilities and realize.The first scheme is: under the condition of catalysts and solvents, compd A and B are first carried out to condensation reaction with propane dinitrile respectively, make aldehyde radical in compd A and B respectively by second dicyano vinyl substituted.Then,, under the condition of catalysts and solvents, the product that condensation reaction generates carries out Stille coupled reaction with Compound C again, obtains described siliceous thiophene organic photoelectrical material.First scheme is: under the condition of catalysts and solvents, compd A and B are first carried out to Stille coupled reaction with Compound C, generation has many thiophene of dialdehyde-based, again many thiophene and propane dinitrile are carried out to condensation reaction, make dialdehyde-based on many thiophene respectively by second dicyano vinyl substituted, obtain described siliceous thiophene organic photoelectrical material.The molar ratio of each reactant can be 1: 1 or other reaction ratio, can carry out the following reaction of the present embodiment, and do not affect reaction carry out.Below be introduced respectively.
The first scheme comprises the steps:
Step I: carry out condensation reaction, under the condition of catalysts and solvents, compd A and B are carried out to condensation reaction with propane dinitrile respectively, make aldehyde radical in compd A and B respectively by second dicyano vinyl substituted, form respectively compd A ' and B ', reaction process is shown below:
Particularly, the catalyzer of step I is pyridine or triethylamine, is preferably pyridine; Solvent is ethanol, methyl alcohol, methylene dichloride, trichloromethane, tetrahydrofuran (THF), ethyl acetate, DMF, toluene or acetone, is preferably ethanol.Wherein, the reaction times is for spending the night, for example 12-14 hour.In addition, after having reacted, then purify, be specially: by after the washing for several times of reaction product saturated sodium-chloride water solution, extract and be dried, after suction filtration, filtrate collection is revolved to steaming, and then carry out silica gel column chromatography separation, obtain purified product.Wherein, extraction agent can adopt ethyl acetate, and siccative can adopt anhydrous magnesium sulfate, and silica gel column chromatography can be at sherwood oil: under the condition that ethyl acetate is leacheate, carry out.In step I, the reacting weight of propane dinitrile is preferably the excessive 30%-70% of total amount (by molecular fraction) of relative compd A and B.
Step I i: under the condition of catalysts and solvents, the compd A ' carry out Stille coupled reaction with B ' together with Compound C that step I is formed, obtains siliceous thiophene organic photoelectrical material, and reaction is shown below:
Particularly, the catalyzer of step I i can be organic palladium catalyzer, for example Pd
2(dba)
3/ P (o-Tol)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, be preferably Pd
2(dba)
3/ P (o-Tol)
3.Solvent can be tetrahydrofuran (THF), methylene dichloride, glycol dimethyl ether, benzene or toluene, is preferably tetrahydrofuran (THF).In step I i, compd A ' and the reacting weight of B ' can be identical molar weight, be preferably the excessive 5%-20% of molar weight (by molecular fraction) of relative Compound C.
After reaction finishes, purify again, be specially: reaction product is returned to room temperature, add KF solution, stirred for several minute, add saturated sodium-chloride water solution, extract again and be dried, after suction filtration, filtrate collection being revolved to steaming, carrying out after twice precipitation with normal hexane and ethanol, filter gained crude product recycle silicon plastic column chromatography and separate, obtain purified product.Wherein, extraction agent can adopt ethyl acetate, and siccative can adopt anhydrous magnesium sulfate, and silica gel column chromatography can be at sherwood oil: under the condition that methylene dichloride is leacheate, carry out.At compd A ' and B ' while carrying out Stille coupled reaction with Compound C, in the time of m ≠ n, compd A in theory ' and B ' self meeting and Compound C generation Stille coupled reaction, form respectively and there is (2m+4) and (2n+4) compound of individual thiphene ring, now, the productive rate that obtains the object product in above-mentioned reaction formula is lower, can obtain the product in pure structural formula by above-mentioned purification step.Be understandable that, now, (2m+4) and (2n+4) compound of individual thiphene ring can be purified out equally, as siliceous thiophene organic photoelectrical material, belongs to the row of the protection structure of the present invention's design.In the time of m=n, compd A ' identical with B ', the productive rate of product is higher, about more than 70%.
First scheme comprises the steps:
Step I ': compd A and B and Compound C are carried out to Stille coupled reaction, generate many thiophene with dialdehyde-based, reaction process is shown below:
Particularly, the step I of this first scheme ' reaction conditions and reaction conditions and the process of the step I i of the first scheme basic identical, this step I ' productive rate is also basic identical with step I i situation, does not repeat them here.
Step I i ': many thiophene with dialdehyde-based and the propane dinitrile of step I ' formation are carried out to condensation reaction, make dialdehyde-based on many thiophene respectively by second dicyano vinyl substituted, obtain above-mentioned siliceous thiophene organic photoelectrical material, reaction process is shown below:
Particularly, reaction conditions and the process of the step I of the reaction conditions of the step I i ' of first scheme and the first scheme are basic identical, do not repeat them here.
In the preparation method of above-mentioned siliceous thiophene organic photoelectrical material, the synthetic route of compd A, B, tri-kinds of monomers of C is fairly simple and ripe, thereby reduces technical process, reduces manufacturing cost.And Stille coupled reaction is a kind of coupled reaction of maturation, productive rate is high, mild condition, is easy to control, and easily improves the solvability of product by introducing alkyl.
The siliceous thiophene organic photoelectrical material of the present embodiment can be applicable in various photoelectricity or semiconducter device, for example, can be used for solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties and organic laser apparatus etc.With solar cell device, organic field effect tube, organic electroluminescence device is that example describes below.Other is as organic light storage device, and organic non-linear optical properties and organic laser apparatus and similar are below all optical memory material, nonlinear material, laserable material or the semiconductor materials etc. using the siliceous thiophene organic photoelectrical material of the present embodiment as it.
Refer to Fig. 2, show the solar cell device that adopts the siliceous thiophene organic photoelectrical material in above-described embodiment, it comprises the glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stack gradually, middle supplementary layer 13 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS), active coating 14 comprises electron donor material and electron acceptor material, electron donor material adopts above-mentioned siliceous thiophene organic photoelectrical material, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM).Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Negative electrode 15 can adopt aluminium electrode, but is not limited to this.Wherein, glass-base 11 can be used as bottom, when making, first by ITO electrodeposition in glass-base 11, then use oxygen-plasma spraying (oxygen-Plasma) treatment process, middle supplementary layer 13 is formed on ITO electrode, and siliceous thiophene organic photoelectrical material and electron acceptor material are deposited on middle supplementary layer 13 by vacuum evaporation technology, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.
As shown in the figure, under illumination, light transmission glass-base 11 and ITO electrode 12, the siliceous thiophene organic photoelectrical material in active coating 14 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission collected by negative electrode, hole is along electron donor material to ito anode transmission collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, when external load 16, can power to it.In this process, siliceous thiophene organic photoelectrical material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as vacuum evaporations, be convenient to large batch of preparation.
Refer to Fig. 3, show the organic electroluminescence device that adopts the siliceous thiophene organic photoelectrical material in above-described embodiment, it comprises the glass-base 21, transparent anode 22, luminescent layer 23, buffer layer 24, the negative electrode 25 that are cascading.Transparent anode 22 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Luminescent layer 23 comprises the siliceous thiophene organic photoelectrical material in above-described embodiment.Buffer layer 24 can adopt LiF etc., but is not limited to this.Negative electrode 25 can be but be not limited to metal A l or Ca, Ba etc., but be not limited to this.Thereby in a specific embodiment, organic electroluminescence device representation is: the siliceous thiophene organic photoelectrical material/LiF/Al of ITO/.Each layer can adopt existing method to form, and siliceous thiophene organic photoelectrical material can be formed on ITO by vacuum evaporation technology.
Refer to Fig. 4, show the organic field effect tube that adopts the siliceous thiophene organic photoelectrical material in above-described embodiment, it comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 being cascading and is located at source electrode 35 and the drain electrode 36 on organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si), and insulation layer 32 can be but be not limited to micro-nano (as 450nm) thick SiO
2.Organic semiconductor layer 34 adopts the siliceous thiophene organic photoelectrical material of foregoing description.Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane alkane.Substrate 31, insulation layer 32, decorative layer 33 and source electrode 35 and drain electrode 36 all can adopt existing method to form.Organic semiconductor layer 34 can be to approach 10 in vacuum tightness
-4under Pa, by the siliceous thiophene organic photoelectrical material evaporation in above-described embodiment on the insulation layer 32 of being modified by decorative layer 33.
Below by specific embodiment illustrate siliceous thiophene organic photoelectrical material preparation method with and the aspect such as performance.The raw material that following embodiment uses can adopt existing synthetic method preparation, for example, bromo-5 '-hexyl-2 of raw material 5-, 2 '-di-thiophene-4-formaldehyde is by 5 '-hexyl-2,2 '-di-thiophene-4-formaldehyde is bromination (reference: " polymer chemistry physics " (Macromol.Chem.Phys.) under NBS condition, 2001,202,2074); 5 '-hexyl-2,2 '-di-thiophene-4-formaldehyde by 5-bromothiophene-3-formaldehyde and 2-hexyl-5-tributyltin chloride thiophene at Pd
2(dba)
3/ P (o-Tol)
3catalytic condition under obtain (reference: " American Chemical Society can will " (J.Am.Chem.Soc.), 1998,120,5355); 4,4 '-bis-(2-ethyl-hexyl)-5,5 '-bis-(tin trimethyl)-bis-thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up by 4,4 '-bis-(2-ethyl-hexyl)-5,5 '-bis-bromo-two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up and reacts with trimethyltin chloride and make (reference: " American Chemical Society can will " (J.Am.Chem.Soc.), 2008,130 (48), 16144).
Embodiment 1
The siliceous thiophene organic photoelectrical material of the present embodiment 1 is with R
1and R
2adopt hexyl, R
3, R
4adopting 2-ethyl-hexyl is example, and its structural formula is as follows:
From this structural formula, the siliceous thiophene organic photoelectrical material of the present embodiment 1 has symmetrical structure, there are six thiphene ring and two pairs of cyano group, cyano group is as electron-withdrawing group, by this kind structure symmetrically, make siliceous thiophene organic photoelectrical material relatively there are good photo absorption performance and photoelectric properties etc.
The preparation method of these connection six thiophene adopts the concrete operations of the first scheme as follows:
1) prepare 2-((the bromo-5-of 2-(5-hexyl thiophene-2-yl) thiene-3-yl-) methylene radical) propane dinitrile, its structural formula is as follows:
Due to, the siliceous thiophene organic photoelectrical material of the present embodiment 1 has symmetrical structure, therefore, the compd A in this step is identical with B structure, and the product of generation is also identical, it is compd A ' identical with B ' structure, only need to carry out one time thus step 1), simplify preparation technology and reduced costs, if siliceous thiophene organic photoelectrical material is not symmetrical structure, compd A is different with B structure so, needs different raw materials carry out step 1).
Its concrete preparation process is: add successively ethanol (50.0mL), bromo-5 '-hexyl-2 of 5-, 2 '-di-thiophene-4-formaldehyde (1.07g, 3.00mmol) and propane dinitrile (0.34g, 5.00mmol), reflux.Add fast 3 pyridines, react 12 hours.With after saturated sodium-chloride water solution washing for several times, ethyl acetate extraction, anhydrous magnesium sulfate drying, revolves steaming by filtrate collection after suction filtration.Be that leacheate carries out silica gel column chromatography separation by petrol ether/ethyl acetate, obtain solid product, productive rate is 65%.
Test result is: MALDI-TOF-MS (m/z): 405.4 (M
+)
2) prepare the siliceous thiophene organic photoelectrical material of the present embodiment, its structural formula is as implied above.
Concrete preparation process is: 40mL THF (tetrahydrofuran (THF)) is added in pressure piping, add fast 2-((the bromo-5-of 2-(5-hexyl thiophene-2-yl) thiene-3-yl-) methylene radical) propane dinitrile (0.89g, 2.20mmol) He 4,4 '-bis-(2-ethyl-hexyls)-5,5 '-bis-(tin trimethyl)-bis-thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up (0.74g, 1.00mmol), nitrogen passes to liquid level following 20 minutes, then adds Pd
2(dba)
3(0.0184g, 0.020mol) and P (o-Tol)
3(0.0122g, 0.040mmol), nitrogen passes to the following deoxygenation of liquid level 20 minutes, and capping is warming up to 80 ℃, reacts 13 hours.After reaction finishes, return to room temperature, add KF (15.0mL, 1.00M) solution, stir 10 minutes, add saturated sodium-chloride water solution, ethyl acetate extraction, anhydrous magnesium sulfate drying, revolves steaming by filtrate collection after suction filtration.By normal hexane and ethanol precipitation, gained crude product is that leacheate carries out silica gel column chromatography separation with sherwood oil/methylene dichloride again, obtains solid product respectively, and productive rate is 71%.
Test result is: MALDI-TOF-MS (m/z): 1067.6 (M
+).
Embodiment 2
The siliceous thiophene organic photoelectrical material of the present embodiment is identical with embodiment 1, but adopts the second to prepare scheme, specific as follows:
1) prepare 2-(2-(3-formyl radical-5-(5-hexyl thiophene-2-yl) thiophene-2-yl)-4; 4 '-bis-(2-ethyl-hexyl)-bis-thiophene [3; 2-b:2 '; 3 '-d] cough up-5-of thiophene yl)-5-(5-hexyl thiophene-2-yl) thiophene-3-formaldehyde, its structural formula is as follows:
Concrete preparation process is: 40mL THF is added in pressure piping, add fast bromo-5 '-hexyl-2 of 5-, 2 '-di-thiophene-4-formaldehyde (0.43g, 1.20mmol) and 4,4 '-bis-(2-ethyl-hexyls)-5,5 '-bis-(tin trimethyl)-bis-thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up (0.74g, 1.00mmol), nitrogen passes to liquid level following 20 minutes, then adds Pd
2(dba)
3(0.0230g, 0.025mmol) and P (o-Tol)
3(0.0152g, 0.050mmol), nitrogen passes to liquid level following 20 minutes, and capping, is warming up to 80 ℃, reacts 14 hours.After reaction finishes, return to room temperature, add KF (15.0mL, 1.00M) solution, stir 20 minutes, add saturated sodium-chloride water solution, ethyl acetate extraction, anhydrous magnesium sulfate drying, revolves steaming by filtrate collection after suction filtration.Be that leacheate carries out silica gel column chromatography separation with sherwood oil/methylene dichloride, obtain solid product, productive rate is 53%.
Test result is: MALDI-TOF-MS (m/z): 971.7 (M
+).
2) prepare the connection six thiophene final products of the present embodiment; concrete preparation process is: add successively ethanol (40.0mL), 2-(2-(3-formyl radical-5-(5-hexyl thiophene-2-yl) thiophene-2-yl)-4; 4 '-bis-(2-ethyl-hexyl)-bis-thiophene [3; 2-b:2 '; 3 '-d] cough up-5-of thiophene yl)-5-(5-hexyl thiophene-2-yl) thiophene-3-formaldehyde (0.97g; 1.00mmol) and propane dinitrile (0.13g; 2.00mmol), reflux.Add fast 4 pyridines, react 12 hours.With after saturated sodium-chloride water solution washing for several times, ethyl acetate extraction, anhydrous magnesium sulfate drying, revolves steaming by filtrate collection after suction filtration.By normal hexane and ethanol precipitation, gained crude product is that leacheate carries out silica gel column chromatography separation with sherwood oil/methylene dichloride again, obtains solid product respectively, and productive rate is 75%.
Test result is: MALDI-TOF-MS (m/z): 1067.5 (M
+).
As from the foregoing, in above-mentioned siliceous thiophene organic photoelectrical material, it has multiple thiphene ring structures, because thiphene ring is five-membered ring structure, meets shock youngster rule, has moderate band gap, wider spectral response, preferably thermostability and environmental stability.And owing to having two pairs of cyano group in above-mentioned siliceous thiophene organic photoelectrical material, cyano group is electron-withdrawing group, can further widen the spectral response range of material, and can improve the photoelectric properties of material.In above-mentioned siliceous thiophene organic photoelectrical material manufacture method, adopt better simply synthetic route, thereby reduce manufacturing cost.Solar cell device, by having adopted siliceous thiophene organic photoelectrical material, can not only improve its photoelectric transformation efficiency, and can alleviate the quality of solar cell device, and is convenient to large batch of preparation.
In addition, in above-mentioned siliceous thiophene organic photoelectrical material, siliceous thiophene unit had both had thiophthene ring structure, also had heterocycle structure, was also a five-membered ring structure, had function and the effect of similar thiphene ring.And two thiphene ring are in same plane, this structure can effectively increase the conjugation performance of molecule, reduces the energy gap of material, expands the absorption region to sunlight, improves the absorption rate to sunlight.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a siliceous thiophene organic photoelectrical material, it comprises the compound that following structural formula (1) represents:
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical integers between 1-10 that is expressed as.
2. siliceous thiophene organic photoelectrical material as claimed in claim 1, is characterized in that described R
1and R
2for identical C
1-C
20straight chained alkyl.
3. siliceous thiophene organic photoelectrical material as claimed in claim 1, is characterized in that described R
3and R
4the identical C that is expressed as
8-C
18alkyl.
4. a siliceous thiophene organic photoelectrical material manufacture method, it comprises the steps:
The compd A, B, C and the propane dinitrile that provide respectively following structural formula to represent,
In formula: R
1, R
2, R
3, R
4identical or different H or the C of being expressed as
1-C
20alkyl; M, n are the identical integers between 1-10 that is expressed as, and An is C
1-C
4alkyl;
Under the condition of catalysts and solvents, compd A and B are carried out to condensation reaction or compd A and B and Compound C are carried out to Stille coupled reaction with propane dinitrile respectively;
Under the condition of catalysts and solvents, the product of condensation reaction and Compound C are carried out to Stille coupled reaction or the product of Stille coupled reaction and propane dinitrile are carried out to condensation reaction, obtain the compound that following structural formula (1) represents:
5. siliceous thiophene organic photoelectrical material manufacture method as claimed in claim 4, it is characterized in that, further compd A and B are carried out to following purification step with the product that propane dinitrile condensation reaction generates respectively: by after the washing for several times of condensation reaction products saturated sodium-chloride water solution, extract and be dried, after suction filtration, filtrate collection is revolved to steaming, then separate with silica gel column chromatography, obtain purified product.
6. siliceous thiophene organic photoelectrical material manufacture method as claimed in claim 4, it is characterized in that, the product further the Stille coupled reaction of compd A and B and Compound C being generated carries out following purification step: in Stille coupled reaction product, add KF solution, stir, add saturated sodium-chloride water solution, extract and be dried, after suction filtration, filtrate collection is revolved to steaming, carry out after twice precipitation with normal hexane and ethanol respectively again, filter gained crude product and separate with silica gel column chromatography, obtain purified product.
7. siliceous thiophene organic photoelectrical material manufacture method as claimed in claim 4, it is characterized in that, the catalyzer that described condensation reaction adopts is pyridine or triethylamine, and the solvent of employing is ethanol, methyl alcohol, methylene dichloride, trichloromethane, tetrahydrofuran (THF), ethyl acetate, DMF, toluene or acetone.
8. siliceous thiophene organic photoelectrical material manufacture method as claimed in claim 4, it is characterized in that, the catalyzer that described Stille coupled reaction adopts is organic palladium catalyzer, and the solvent of employing is tetrahydrofuran (THF), methylene dichloride, glycol dimethyl ether, benzene or toluene.
9. the siliceous thiophene organic photoelectrical material as described in claim 1-3 any one is in the application of manufacturing in solar cell device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties or organic laser apparatus.
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