WO2011091609A1 - 含杂环醌型噻吩有机光电材料、其制备方法和应用 - Google Patents

含杂环醌型噻吩有机光电材料、其制备方法和应用 Download PDF

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WO2011091609A1
WO2011091609A1 PCT/CN2010/070438 CN2010070438W WO2011091609A1 WO 2011091609 A1 WO2011091609 A1 WO 2011091609A1 CN 2010070438 W CN2010070438 W CN 2010070438W WO 2011091609 A1 WO2011091609 A1 WO 2011091609A1
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organic
heterocyclic
organic photoelectric
photoelectric material
thiophene
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PCT/CN2010/070438
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English (en)
French (fr)
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周明杰
黄杰
刘辉
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海洋王照明科技股份有限公司
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Priority to EP10844387.0A priority Critical patent/EP2530085B1/en
Priority to US13/575,699 priority patent/US8735605B2/en
Priority to PCT/CN2010/070438 priority patent/WO2011091609A1/zh
Priority to JP2012550294A priority patent/JP5480404B2/ja
Priority to CN2010800481035A priority patent/CN102574867B/zh
Publication of WO2011091609A1 publication Critical patent/WO2011091609A1/zh

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Definitions

  • the present invention relates to the field of organic material technology, and in particular to a heterocyclic quinone-containing thiophene.
  • the organic photoelectric material its preparation method and application.
  • Organic solar cells are a new type of solar cells. Compared with inorganic semiconductor materials, which are limited in source, expensive, toxic, complicated in preparation process and high in cost, they have some advantages that inorganic solar cells cannot match, such as a wide range of materials. Structure diversity and controllability, low cost, safety and environmental protection, simple production process, light weight, large area flexible preparation, etc., can be widely used in various fields such as construction, lighting and power generation, with important development and application. prospect. Therefore, many research institutions and enterprises at home and abroad have given considerable attention and input. However, so far, the photoelectric conversion efficiency of organic solar cells is still much lower than that of inorganic solar cells. Therefore, the development of new organic optoelectronic materials is important for improving the efficiency of organic solar cells and other semiconductor devices. To sense t SUMMARY
  • a heterocyclic thiophene-containing thiophene having a broad response to light and stability is provided. It is divided into organic photoelectric materials, and a heterocyclic hydrazine-containing thiophene with a simple synthetic route and low cost.
  • a method for preparing an organic photoelectric material is provided.
  • the present invention also provides the above heterocyclic hydrazine-containing thiophene.
  • organic optoelectronic materials in the preparation of solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical memory devices, organic nonlinear materials or organic laser devices.
  • An organic photoelectric material comprising a compound represented by the following structural formula (1):
  • R 2 , R 5 , R 6 are alkyl or alkoxy groups which are the same or differently represented as H or dC ⁇ , and R 3 and R 4 are alkyl or alkane which are identical or differently represented as CrC ⁇ A, b is the same or differently expressed as an integer between 1 and 12; X is Si or C.
  • a thiophene containing a heterocyclic ring comprising the steps of:
  • R 2 , R 5 , R 6 are alkyl or alkoxy groups which are the same or differently represented as H or dC ⁇ o, and R 3 , which is the same or differently represented as -C 2 ( alkyl or alkoxy group; a, b are the same or differently expressed as an integer between 1 and 12; X is Si or C, and An is an alkyl group of d-C4;
  • the compound, B, and C are subjected to Stille coupling reaction under the conditions of a catalyst and a solvent; the Stille coupling reaction product is subjected to a bromination substitution reaction to form a brominated product;
  • the bromination product is subjected to a condensation reaction with malononitrile under the conditions of a catalyst, a condensing agent and a solvent to obtain a compound represented by the following structural formula (1):
  • organic optoelectronic materials in the preparation of solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical memory devices, organic nonlinear materials or organic laser devices.
  • the unitary thiophene structure of the unit expands the conjugate structure and increases the planarity of the molecule, which is beneficial to reduce the energy gap of the material, thereby further widening the absorption range of the material to the solar term, for example, the absorption band edge of the material Pushing into the red and near-infrared regions, thereby improving the photoelectric properties and photoelectric conversion efficiency of the material.
  • heterocyclic quinone type thiophene In the above-mentioned heterocyclic quinone type thiophene.
  • a simple synthesis route and Stille coupling reaction can be used to simplify the process and reduce the production cost.
  • FIG. 1 is a heterocyclic quinone-containing thiophene of an embodiment of the present invention.
  • Structural formula of organic photoelectric material compound (1) Schematic diagram
  • Fig. 2 is a heterocyclic anthracene type thiophene according to an embodiment of the present invention.
  • a flow chart of a method for preparing an organic photoelectric material and
  • Fig. 3 is a heterocyclic anthracene type thiophene according to an embodiment of the present invention. Schematic diagram of the structure of a solar cell device divided into organic photoelectric materials.
  • Figure 4 is a heterocyclic hydrazine-containing thiophene employing an embodiment of the present invention. Schematic diagram of the structure of an organic electroluminescent device classified into an organic photoelectric material.
  • Figure 5 is a heterocyclic hydrazine-containing thiophene using an embodiment of the present invention. Schematic diagram of the structure of an organic field photovoltaic transistor with an organic photoelectric material. detailed description
  • R 2 , R 5 , R 6 are alkyl or alkoxy groups which are the same or differently represented as H or dC ⁇ , and R 3 and R 4 are the same or differently represented as an alkyl group of CrC ⁇ or Alkoxy; a, b are the same or differently expressed as an integer between 1 and 12; X is Si or C.
  • a heterocyclic quinone type thiophene is included.
  • the organic photoelectric material has a symmetrical molecular structure.
  • the molecular weight of the organic photoelectric material is small, and the quality of the produced product is light.
  • R 6 is the same 11, dC alkyl or alkoxy
  • R 2 and R 5 are the same CrC alkyl or alkoxy.
  • R 3 is the same d- o alkyl or Alkoxy.
  • R 2 , R 5 and R 6 are all H
  • R 3 and R 4 are each a C 6 or C 6 alkyl group.
  • heterocyclic quinone type thiophene In the above-mentioned heterocyclic quinone type thiophene. In the organic photoelectric material, it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, and has a wide optical response, and the band is about 300-750. Nm, basically covers the visible light band. In addition, it also has good thermal stability and environmental stability, and exhibits good photoelectric properties. Further, the above-mentioned heterocyclic quinone-containing thiophene.
  • the unitary thiophene structure of the unit expands the conjugate structure and increases the planarity of the molecule, which is beneficial to reduce the energy gap of the material, thereby further widening the absorption range of the material to the solar spectrum, for example, pushing the absorption band edge of the material.
  • the red light and the near-infrared region are increased to improve the photoelectric performance and photoelectric conversion efficiency of the material.
  • both R 3 and R 4 are alkyl or alkoxy groups, which can improve the solubility of the material, increase the molecular weight of the material, and facilitate the film formation process and expand the application range. .
  • the method for preparing the organic photoelectric material comprises the following steps: S01: providing compounds A, B, C and malononitrile represented by the following structural formulas, respectively
  • R 2 , R 5 , R 6 are alkyl or alkoxy groups which are the same or differently represented as H or dC ⁇ o, and R 3 and R 4 are alkyl or alkoxy groups which are the same or differently represented by -C20; a, b are the same or differently expressed as an integer between 1 and 12; X is Si or C, and An is an alkyl group of d-C4;
  • step S01 compounds A, B, C and malononitrile are commercially available or can be prepared by existing synthetic methods and will not be described in detail herein.
  • the structures in the compounds A, B and C are the same as the above-mentioned heterocyclic quinone-containing thiophenes.
  • the description of the organic photoelectric materials is basically the same and will not be described in detail herein.
  • An may be an alkyl group having a decyl group, an n-butyl group or a tert-butyl group as d-C4.
  • the catalyst used in the Stille coupling reaction is an organic palladium catalyst, such as Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 , etc., preferably Is Pd 2 (dba) 3 /P(o-Tol) 3 .
  • the solvent may be tetrahydrofuran, dichlorodecane, ethylene glycol dioxime ether, benzene or toluene, etc., preferably tetrahydrofuran.
  • the compound A, B, and C may be added in an amount of from 1% to 20% by weight based on the chemical reaction, or the compounds A and B are not limited thereto.
  • the reaction is as follows:
  • step S02 The specific implementation process of step S02 is as follows: Under anhydrous nitrogen, anhydrous THF is added to the pressure resistant tube, and the compounds A and B and the compound C are quickly added, and after bubbling for several tens of minutes, the organic palladium catalyst is added, capped, and the temperature is raised to At 80 ° C, reflux for 24 hours.
  • KF such as 1.00 M
  • aqueous solution is added to the reaction product, stirred for several tens of minutes, added with a saturated aqueous solution of sodium chloride, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and evaporated. Chromatographic separation gave the product.
  • the solvent may be dimercaptophthalamide (DMF), tetrahydrofuran, carbon tetrachloride, chloroform, dichlorodecane or acetonitrile, and the like, and N-bromosuccinimide (NBS), Br is added. 2 , HBr or PBr 3, etc., preferably NBS.
  • DMF dimercaptophthalamide
  • NBS N-bromosuccinimide
  • the catalyst is an organic palladium catalyst such as Pd 2 (dba) 3 /P(o-Tol) 3 , Pd(PPh 3 ) 4 or Pd(PPh 3 ) 2 Cl 2 or the like, preferably PdCl 2 (PPh) 3 ) 2
  • the solvent used may be ethylene glycol diterpene ether, ethanol, decyl alcohol, dichlorodecane, trichlorodecane, tetrahydrofuran, ethyl acetate, DMF, toluene or acetone, preferably ethylene glycol Ether ether.
  • the condensing agent may be sodium hydride or sodium alkoxide, and the sodium alkoxide may be, for example, sodium decoxide or Sodium butoxide or the like is preferably sodium hydride.
  • step S03 The specific implementation process is as follows: Add malononitrile to a suspension of sodium hydride (60% in oil) and ethylene glycol dioxime (DME) under ice bath, return to room temperature, stir for 30 minutes, and add to step S03.
  • the obtained brominated product and the organic palladium catalyst were heated to reflux for 12 hours, cooled to 0 ° C, added with a saturated Br 2 /H 2 0 solution, added with water, suction filtered, washed with water, dried, and then purified by silica gel column chromatography. .
  • the synthesis routes of the three monomers of the compounds A, B and C are relatively simple and mature, thereby reducing the process flow and reducing the preparation cost.
  • the Stille coupling reaction is a mature coupling reaction with high yield, mild conditions, easy control, and easy introduction of alkyl or alkoxy groups to improve the solubility of the product, which is beneficial to the processing properties of the material.
  • the heterocyclic anthracene type thiophene of this embodiment The organic optoelectronic material can be applied to various optoelectronic or semiconductor devices, for example, for solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical storage devices, organic nonlinear materials, and organic laser devices.
  • a solar cell device, an organic field effect transistor, and an organic electroluminescence device will be described as an example.
  • Others such as organic optical storage devices, organic nonlinear materials and organic laser devices are similar to the following, and are all the heterocyclic quinone-containing thiophenes of this embodiment.
  • the organic photoelectric material is classified as an optical storage material, a nonlinear material, a laser material or a semiconductor material.
  • a solar cell device having an organic photoelectric material comprising a glass base layer 11 sequentially laminated, a transparent anode 12, an intermediate auxiliary layer 13,
  • the active layer 14, the cathode 15, and the intermediate auxiliary layer 13 are made of polyethylene dioxythiophene: polystyrene-sulfonic acid composite (abbreviated as PEDOT:PSS), and the active layer 14 includes an electron donor material and an electron acceptor material, and electrons.
  • PEDOT:PSS polystyrene-sulfonic acid composite
  • the donor material adopts the above heterocyclic quinone-containing thiophene organic photoelectric material, and the electron acceptor material may be
  • the transparent anode 12 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the cathode 15 can be an aluminum electrode.
  • the glass base layer 11 can be used as a bottom layer. When fabricated, an ITO electrode is first deposited on the glass base layer 11, and an intermediate-assisted layer 13 is formed on the ITO electrode by an oxygen-plasma treatment process, and Heterocyclic thiophene.
  • the organic photoelectric material and the electron acceptor material are deposited on the intermediate auxiliary layer 13 by a vacuum evaporation technique to form the active layer 14, and then the cathode 15 is deposited on the active layer 14 by a vacuum evaporation technique to obtain the above solar cell device.
  • the active layer 14 contains a heterocyclic thiophene.
  • the organic optoelectronic material absorbs light energy and generates excitons, which then migrate to the interface of the electron donor/acceptor material, and transfer the electrons to an electron acceptor material, such as PCBM, to separate the charge, thereby forming Free carriers, ie free electrons and holes. These free electrons are transferred to the metal cathode along the electron acceptor material and collected by the cathode. Free holes are transported along the electron donor material to the ITO anode and collected by the anode, thereby forming photocurrent and photovoltage for photoelectric conversion, external connection. When the load is 16, it can be powered.
  • a heterocyclic quinone type thiophene is included.
  • the organic optoelectronic material has a wider optical response range, which enables the light energy to be more fully utilized to obtain higher photoelectric conversion efficiency and increase the power generation capability of the solar cell device.
  • the organic material can also reduce the quality of the solar cell device and can be fabricated by techniques such as vacuum evaporation, which facilitates mass production.
  • An organic electroluminescent device of an organic photoelectric material comprising a glass base layer 21, a transparent anode 22, a light-emitting layer 23, a buffer layer 24, and a cathode 25 which are laminated in this order.
  • the transparent anode 22 may be indium tin oxide (abbreviated as ITO), preferably indium tin oxide having a sheet resistance of 10-20 ⁇ /.
  • the light-emitting layer 23 contains the heterocyclic anthracene-type thiophene in the above examples. Divided into organic photoelectric materials.
  • the buffer layer 24 may be LiF or the like, but is not limited thereto.
  • the cathode 25 may be, but not limited to, metal A1 or Ba or the like, but is not limited thereto.
  • organic electricity The structure of the electroluminescent device is expressed as: ITO/heterocyclic thiophene. Divided into organic photoelectric material / LiF / Al. Each layer can be formed by an existing method and contains a heterocyclic quinone type thiophene. The organic optoelectronic material can be formed on ITO by vacuum evaporation.
  • An organic field-effect transistor having an organic photoelectric material includes a substrate 31, an insulating layer 32, a modifying layer 33, an organic semiconductor layer 34, and a source electrode 35 and a drain electrode 36 provided on the organic semiconductor layer 34.
  • the substrate 31 may be, but not limited to, a highly doped silicon wafer (Si), and the insulating layer 32 may be, but not limited to, a micro-nano (eg, 450 nm) thick SiO 2 .
  • the organic semiconductor layer 34 employs the heterocyclic quinone-containing thiophene organic photoelectric material described above.
  • Both the source electrode 35 and the drain electrode 36 may be, but not limited to, gold.
  • the modifying layer 33 can be, but is not limited to, octadecyltrichlorosilane.
  • the substrate 31, the insulating layer 32, the trim layer 33, and the source electrode 35 and the drain electrode 36 can be formed by a conventional method.
  • the organic semiconductor layer 34 may be formed by vapor-depositing the heterocyclic fluorene-containing thiophene-containing organic photoelectric material in the above embodiment on the insulating layer 32 modified by the modification layer 33 at a vacuum degree close to 1 (T 4 Pa).
  • the heterocyclic indole type thiophene is exemplified below by way of specific examples. Divided into organic photoelectric materials preparation methods and their properties.
  • the materials used in the following examples can be prepared by a conventional synthesis method, for example, the following starting material 4, 4,-dihexyl-4 /-cyclopentane [2, 1-b: 3, 4-b,] Dithiophene is prepared from 4 /-cyclopentane [2, 1-b: 3, 4-b,] dithiophene and 1-bromohexane.
  • 4 4,-dihexyl-4 /-cyclopentane [2, 1-b: 3, 4-b,]
  • Dithiophene is prepared from 4 /-cyclopentane [2, 1-b: 3, 4-b,] dithiophene and 1-bromohexane.
  • Polymer Polymer
  • Silane consists of 3,3,-dibromo-5,5,-bis(trimethylsilyl)-2,2,-bithiophene. It is prepared with butyl lithium and dichlorobis(2-ethyl-hexyl)-silane.
  • 2,-dithiophene is prepared by the catalytic action of 2-bromothiophene under Ni(dppp)Cl 2 .
  • the heterocyclic hydrazine-containing thiophene of the first embodiment is as follows:
  • the structure is such that it contains a heterocyclic quinone type thiophene.
  • the organic photoelectric material has relatively good light absorption performance and photoelectric performance, and the molecular weight is small, and the quality of the produced product is light.
  • the heterocyclic quinone-containing thiophene of this Example 1 The specific process for preparing the organic photoelectric material is as follows: 1) Preparation of 4, 4,-dihexyl-2,6-dibromo-4 /-cyclopentane [2, 1-b: 3, 4-b,] Thio.
  • the structural formula is as follows:
  • test results were: MALDI-TOF-MS (m/z): 504.4 (M + ).
  • test results were: MALDI-TOF-MS (m/z): 672.2 (M + ).
  • this step i.e., the aforementioned step S02
  • the structures of the compounds A and B are the same (for example, both are 2-bromothiophene)
  • the source of the raw material can be simplified, thereby simplifying the preparation process and reducing the cost.
  • this step has a higher yield than when different compounds A and B are employed.
  • the specific preparation process is as follows: Under the protection of nitrogen, 25 mL of anhydrous THF is added to the pressure resistant tube, and 2.02 g of 4,4,-dihexyl-2,2,-bis(trimethyltinyl)-4/ -cyclopentane [2, 1-b: 3, 4-b,] dithiazide Phenol and 1.08 g of 2-bromothiophene were added. After bubbling for 30 minutes, 0.056 g of Pd 2 (dba) 3 and 0.040 g of P(o-Tol) 3 were added , capped, and the temperature was raised to 80 ° C and refluxed for 26 hours. After completion of the reaction, 15.0 mL of aq. KF (1.00 M) was added, and the mixture was stirred for 30 minutes, and then a saturated aqueous solution of sodium chloride, ethyl acetate, and dried over anhydrous magnesium sulfate.
  • the specific preparation process is as follows: 0.78 g of NBS is added in portions to 1.02 g of 4,4,-dihexyl-2,6-bis(thiazol-2-yl)-4 in an ice bath and protected from light. /-Cyclopentane [2, 1-b: 3, 4-b,] dithiophene and 20 mL DMF in a reaction flask, stirred at room temperature for 12 hours. After the completion of the reaction, the reaction mixture was poured into ice water to give a mixture. The mixture was evaporated, evaporated, evaporated.
  • the specific preparation process is: adding 0.20 g of malononitrile to a suspension of 0.24 g of sodium hydride (60% in oil) and 20 mL of ethylene glycol dioxime under ice bath, returning to room temperature, stirring for 30 minutes, adding 0.72 g of 2,6-bis(5-bromo-thiazol-2-yl)-dithiophene [3,2-b,3'-d] thiophene and 0.038 g of PdCl 2 (PPh 3 ) 2o heated to reflux After 14 hours, it was cooled to 0 ° C and a saturated Br 2 /H 2 0 solution was added. Water was added, suction filtration, washing with water, and dried.
  • the heterocyclic quinone-containing thiophene of this Example 2 The structure of the organic photoelectric material is as follows:
  • the structural formula is similar to that of the embodiment 1, and has a symmetric structure, and R 2 , R 5 and R 6 are all H, except that R 3 , R 4 are 2-ethyl-hexyl, X is Si, and have six.
  • the heterocyclic anthracene type thiophene of this embodiment is as follows: 1) Preparation of 5-bromo-2,2'-bidithiophene, as the compounds A and B of this example, the structural formula is as follows:
  • the organic photoelectron material is not a symmetrical structure, and if the structures of the compounds A and B are different, it is necessary to carry out the steps 2) for the different materials.
  • the specific preparation steps were as follows: 17.80 g of NBS was added in portions to a reaction flask containing 16.60 g of 2,2,-dithiophene and 200 mL of DMF in an ice bath and protected from light, and stirred at room temperature for 12 hours. After the reaction is completed, the reaction solution is poured into ice water and quenched, extracted with trichloromethane, dried over anhydrous magnesium sulfate, and then evaporated. The product was isolated by gel column chromatography.
  • test results were: MALDI-TOF-MS (m/z): 245.2 (M + ).
  • the specific preparation steps are as follows: 16.90 g of 4,4,-bis(2-ethyl-hexyl)-5,5,-bis(trimethylsilyl)-dithio.
  • the [3, 2-b: 2,, 3,-d] silane was dissolved in 200 mL of tetrahydrofuran, and 11.00 g of NBS was added in portions and stirred at room temperature for 6 hours. The reaction was completed, extracted with diethyl ether, dried over anhydrous sodium sulfate, filtered, and evaporated.
  • test results were: MALDI-TOF-MS (m/z): 576.6 (M + ).
  • the specific preparation steps are as follows: 11.52 g of 4,4,-bis(2-ethyl-hexyl)-5,5,-dibromo-dithiophene [3, 2-b:2,,3,-d] silane is added. And anhydrous 100.0 mL of THF solution, 17.8 mL of n-butyllithium solution (2.7 M n-hexane solution) was added dropwise at -25 °C. After stirring for 2 hours, 9.71 g of trimethyltin chloride was added dropwise, and stirring was continued for 6 hours. After the reaction is completed, the reaction solution is returned to room temperature, and saturated ammonium chloride water is added. The solution was extracted with diethyl ether, dried over anhydrous magnesium sulfate and evaporated. After this step is completed, you do not need to purify and proceed directly to the next step.
  • the specific preparation process is as follows: Under the protection of nitrogen, 80 mL of anhydrous THF is added to the pressure resistant tube, and 7.44 g of 4,4,-bis(2-ethyl-hexyl)-5,5,-bis (triterpene) is quickly added. Tin-)dithiophene [3,2-b:2', 3,-d] silane and 5.40 g of 5-bromo-2, 2,-bi-dithiophene. After 30 minutes of bubbling, 0.19 g of Pd 2 (dba) 3 and 0.14 g of P(o-Tol) 3 were added , and the mixture was capped, heated to 80 ° C, and refluxed for 24 hours. After the reaction was completed, a solution of 30.0 mL of KF (1.00 M) was added, and the mixture was stirred for 40 minutes, and then aq.
  • the specific preparation process is as follows: 3.92 g of NBS is added in portions to 3.74 g of 2,6-bis(2,2,-dithiophen-5-yl)-4, 4 in an ice bath and protected from light. - A reaction flask of bis(2-ethyl-hexyl)-dithiophene [3, 2-b: 2', 3,-d] silane and 50 mL of DMF was stirred at room temperature for 12 hours. After the completion of the reaction, the reaction mixture was poured into ice water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and evaporated.
  • test results were: MALDI-TOF-MS (m/z): 905.1 (M + ).
  • the specific preparation process is as follows: 0.16 g of malononitrile is added to a suspension of 0.20 g of sodium hydride (60% in oil) and 30 mL of ethylene glycol dioxime in an ice bath, returned to room temperature, stirred for 40 minutes, and added. 1.81 g 2,6-bis(5,-bromo-2, 2,-bidithiophen-5-yl)-4,4,-bis(2-ethyl-hexyl)-dithiophene [3, 2-b : 2', 3'-d] silane and 0.070 g PdCl 2 (PPh 3 ) 2 . After heating to reflux for 12 hours, it was cooled to 0 ° C and a saturated Br 2 /H 2 0 solution was added. Water was added, suction filtration, washing with water, and dried.
  • the above-mentioned heterocyclic quinone-containing thiophene is known.
  • the organic photoelectric materials it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, a wide optical response, and good thermal stability. And environmental stability.
  • the above-mentioned heterocyclic quinone-containing thiophene is known.
  • the organic photoelectric materials it has a plurality of quinone thiophene ring structures, because the thiophene ring is a five-membered ring structure, conforms to the shock rule, has a moderate band gap, a wide optical response, and good thermal stability. And environmental stability.
  • the above-mentioned heterocyclic quinone-containing thiophene is known.
  • the thiophene ring is a five-membered ring structure, conforms to the shock rule,
  • the planarity of the molecule is beneficial to reduce the energy gap of the material, thereby further widening the absorption range of the material to the solar term, for example, The absorption band edge of the material is pushed toward the red and near-infrared regions, thereby improving the photoelectric properties and photoelectric conversion efficiency of the material.
  • heterocyclic quinone type thiophene In the above-mentioned heterocyclic quinone type thiophene.
  • organic photoelectric material In the preparation method of the organic photoelectric material, the simple synthesis route and the Stille coupling reaction can simplify the process and reduce the production cost.
  • the above heterocyclic quinone type thiophene When organic photoelectric materials are used in solar cell devices, organic field effect transistors, organic electroluminescent devices, organic optical storage devices, organic nonlinear materials or organic laser devices, their photoelectric or semiconductor-related properties can be improved, and devices can be lightened. The quality is easy to prepare in large quantities.

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Description

含杂环醌型噻吩有机光电材料、 其制备方法和应用
技术领域 本发明属于有机材料技术领域， 具体涉及一种含杂环醌型噻。分有机光电材 料、 其制备方法和应用。
说 背景技术
当今世界经济主要是建立在以化石能源， 如煤炭、 石油和天然气等基石出之 上的经济。然而，这些不可再生的化石能源都在书不断的枯竭。进入 21世纪以来， 全球性的能源问题以及随之而来的环境污染和气候变暖等问题日益凸现和逐渐 加剧。 由于太阳能具有分布普遍和广阔， 资源数量多， 无污染， 清洁， 安全以 及获取方便等突出优点， 被认为是最有希望的可再生能源之一。 太阳能电池直 接把太阳光能转化成电能， 是利用太阳能切实可行的有效方法。 然而， 目前商 品化的太阳能电池还局限于硅基等无机太阳能电池， 但它们的价格过于昂贵， 超出了目前人们普遍可以接受的程度， 这大大限制了它们的使用范围。 为了降 低电池成本， 拓展应用范围， 长期以来， 人们一直在寻找新型的太阳能电池材 料。
有机太阳能电池是一种新型的太阳能电池， 相对于无机半导体材料来源有 限、 价格昂贵、 有毒、 制备工艺复杂、 成本太高等而言， 它具有无机太阳能电 池无法比拟的一些优点， 如材料来源广泛、 结构多样性和可调控性、 成本低廉、 安全环保、 制作工艺简单、 产品重量轻、 可大面积柔性制备等等， 可以广泛应 用在建筑、 照明和发电等多种领域， 具有重要的发展和应用前景。 因此， 国内 外众多的研究机构和企业等都给予了相当的关注和投入。 然而， 到目前为止， 有机太阳能电池的光电转换效率比无机太阳能电池还是要低 4艮多。 因此， 开发 新型的有机光电材料对于提高有机太阳能电池及其它半导体器件的效率具有重 要意义 t 发明内容
有鉴于此， 提供一种光语响应宽、 稳定性好的含杂环醌型噻。分有机光电材 料， 以及一种合成路线简单、成本低的含杂环醌型噻。分有机光电材料制备方法。
本发明实施例还提供上述含杂环醌型噻。分有机光电材料在制备太阳能电池 器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性 材料或有机激光器件中的应用。
一种含杂环醌型噻。分有机光电材料，其包含如下结构式（ 1 )表示的化合物：
Figure imgf000004_0001
式中：： R2、 R5、 R6是相同或不同地表示为 H或 d-C^的烷基或烷氧 基， R3、 R4是相同或不同地表示为 CrC^的烷基或烷氧基； a、 b是相同或不同 地表示为 1-12之间的整数； X为 Si或 C。
一种含杂环醌型噻。分有机光电材料制备方法， 其包括如下步骤：
分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000004_0002
R2、 R5、 R6是相同或不 同地表示为 H或 d-C^o的烷基或烷氧基， R3、 是相同或不同地表示为 -C2( 的烷基或烷氧基； a、 b是相同或不同地表示为 1-12之间的整数； X为 Si或 C, An为 d-C4的烷基； 在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应； 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物；
在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反应, 获得如下结构式 ( 1 )表示的化合物：
Figure imgf000005_0001
以及， 上述含杂环醌型噻。分有机光电材料在制备太阳能电池器件、 有机场 效应晶体管、 有机电致发光器件、 有机光存储器件、 有机非线性材料或有机激 光器件中的应用。
在上述含杂环醌型噻。分有机光电材料中， 其具有多个醌型噻吩环结构， 由 于噻吩环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽的光谱响 应， 较好的热稳定性和环境稳定性。 而且， 上述含杂环醌型噻。分有机光电材料 在分子的两端引入强吸电子基团二氛基乙婦基（ = C(CN)2 ),成为含二噻吩并噻 。分单元的醌型噻吩结构， 扩大了共轭结构， 增加了分子的平面性， 有利于降低 材料的能隙， 从而进一步加宽材料对太阳光语的吸收范围， 例如可将材料的吸 收带边沿推向红光及近红外区， 从而提高材料的光电性能和光电转换效率。 在 上述含杂环醌型噻。分有机光电材料制备方法中，采用较简单的合成路线和 Stille 耦合反应， 可简化工艺和降低制备成本。 上述含杂环醌型噻吩有机光电材料应 用于太阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器 件、 有机非线性材料或有机激光器件中时， 可提高其光电或半导体相关性能， 并能减轻器件的质量， 且便于大批量的制备。 附图说明
下面将结合附图及实施例对本发明作进一步说明， 附图中：
图 1是本发明实施例的含杂环醌型噻。分有机光电材料化合物的结构式（ 1 ) 的示意图；
图 2是本发明实施例的含杂环醌型噻。分有机光电材料制备方法流程图； 图 3是采用本发明实施例的含杂环醌型噻。分有机光电材料的太阳能电池器 件结构示意图。
图 4是采用本发明实施例的含杂环醌型噻。分有机光电材料的有机电致发光 器件的结构示意图。
图 5是采用本发明实施例的含杂环醌型噻。分有机光电材料的有机场效应晶 体管的结构示意图。 具体实施方式
为了使本发明的目的、 技术方案及优点更加清楚明白， 以下结合附图及实 施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体实施例仅 仅用以解释本发明， 并不用于限定本发明。
请参阅图 1 , 显示本发明实施例的含杂环醌型噻。分有机光电材料化合物的 结构式（ 1 ) , 即包含如下结构式（ 1 )表示的化合物：
Figure imgf000006_0001
式中：： 、 R2、 R5、 R6是相同或不同地表示为 H或 d-C^的烷基或烷氧 基， R3、 R4是相同或不同地表示为 CrC^的烷基或烷氧基； a、 b是相同或不同 地表示为 1-12之间的整数； X为 Si或 C。
在本发明的一个实施例中， 含杂环醌型噻。分有机光电材料具有对称的分子 结构。 例如， a、 b是相同的表示为 1-12之间的整数， 即 a=b。 在一个优选的实 施例中， a=b=l或 2, 此时， 该含杂环醌型噻。分有机光电材料分子量较小， 制成 的产品质量较轻。 在本发明一个实施例中， 、 R6为相同的 11、 d-C^烷基或 烷氧基， R2、 R5为相同的 CrC^烷基或烷氧基。 R3、 为相同的 d- o烷基或 烷氧基。 这样的结构可以简化制备工艺， 降低生产成本。 在本发明一个优选的 实施例中， R2、 R5、 R6均为 H, R3、 R4均为 C6或 C6以上的烷基。
在上述含杂环醌型噻。分有机光电材料中， 其具有多个醌型噻吩环结构， 由 于噻吩环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽的光语响 应， 波段大约在 300-750 nm, 基本涵盖可见光波段。 另外， 还具有较好的热稳 定性和环境稳定性， 表现出较好的光电性能。 而且， 上述含杂环醌型噻。分有机 光电材料在分子的两端引入强吸电子基团二氛基乙烯基（ = C(CN)2 ),成为含二 噻吩并噻。分单元的醌型噻吩结构， 扩大了共轭结构， 增加了分子的平面性， 有 利于降低材料的能隙， 从而进一步加宽材料对太阳光谱的吸收范围， 例如可将 材料的吸收带边沿推向红光及近红外区， 从而提高材料的光电性能和光电转换 效率。 另外， R3、 R4均采用烷基或烷氧基， 可提高材料的溶解性， 增加材料的 分子量， 并有利于成膜加工， 扩大其应用范围。 。
请参阅图 2, 上述含杂环醌型噻。分有机光电材料的制备方法包括如下步骤： S01 : 分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000007_0001
、 R2、 R5、 R6是相同或不 同地表示为 H或 d-C^o的烷基或烷氧基， R3、 R4是相同或不同地表示为 -C20 的烷基或烷氧基； a、 b是相同或不同地表示为 1-12之间的整数； X为 Si或 C, An为 d-C4的烷基；
S02: 在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应；
S03: 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物；
S04: 在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反 应， 获得如下结构式 (1)表示的化合物:
Figure imgf000008_0001
在步骤 S01 中， 化合物 A、 B、 C以及丙二腈可直接从市场上购得或者通 过现有的合成方法制备， 在此不再详述。 其中， 化合物 A、 B、 C中的结构与上 述含杂环醌型噻。分有机光电材料的描述基本一致， 在此不再详述。 其中， 需要 说明的是， An可以是曱基、 正丁基或叔丁基为 d-C4的烷基。
在步骤 S02 中， Stille 耦合反应采用的催化剂为有机钯催化剂， 例如 Pd2(dba)3/P(o-Tol)3, Pd(PPh3)4或 Pd(PPh3)2Cl2等， 优选为 Pd2(dba)3/P(o-Tol)3。 溶剂可以是四氢呋喃、 二氯曱烷、 乙二醇二曱醚、 苯或曱苯等， 优选为四氢呋 喃。 化合物 A、 B、 C的加入量可以是按照化学反应计量， 或者是化合物 A、 B 采用过量 1%-20%的摩尔量， 并不限于此。 其反应如下式所示：
Figure imgf000008_0002
步骤 S02的具体实施过程如下： 在氮气保护下， 将无水 THF加入至耐压管 中，快速加入化合物 A和 B 以及化合物 C,鼓泡数十分钟后加入有机钯催化剂， 封盖， 升温至 80°C , 回流 24小时。 反应结束， 再进行如下提纯步骤： 往反应 产物中加入 KF (如 1.00 M) 水溶液， 搅拌数十分钟， 加入饱和氯化钠水溶液， 乙酸乙酯萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。 进行 Stille耦合反应时， 当 a≠b时， 理论上化合物 A和 B自身会与化合物 C发生 Stille耦合反应， 分别形成具有 （2a+2 )和（ 2b+2 )个噻吩环的化合物。 此时， 得到上述反应式中的目的产物的产率较低， 可通过上述提纯步骤来获得 纯的结构式中的产物。 可以理解的是， 此时， （2a+2 )和（2b+2 )个噻吩环的 化合物同样可提纯出， 作为含杂环醌型噻。分有机光电材料， 属于本发明构思的 保护结构之列。 当 a=b时， 化合物 A和 B相同， 目的产物的产率较高。
在步骤 S03中， 溶剂可采用二曱基曱酰胺（DMF )、 四氢呋喃、 四氯化碳、 氯仿、 二氯曱烷或乙腈等， 并加入 N-溴代丁二酰亚胺（NBS ) 、 Br2、 HBr或 PBr3等， 优选为 NBS。 其反应如下式所示：
Figure imgf000009_0001
具体实施过程如下： 在冰浴、 避光条件下， 将 NBS 分批加入至盛有步骤 S02生成的产物和 DMF的反应器中， 室温搅拌 12小时。 反应结束， 将反应液 倒入冰水中淬灭， 三氯曱烷萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得 到产物。
在步骤 S04中，催化剂为有机钯催化剂，例如 Pd2(dba)3/P(o-Tol)3、 Pd(PPh3)4 或 Pd(PPh3)2Cl2等， 优选为 PdCl2(PPh3)2, 采用的溶剂可以为乙二醇二曱醚、 乙 醇、 曱醇、 二氯曱烷、 三氯曱烷、 四氢呋喃、 乙酸乙酯、 DMF、 曱苯或丙酮， 优选为乙二醇二曱醚。 缩合剂可以是氢化钠或醇钠， 醇钠可以是例如曱醇钠或 叔丁醇钠等， 优选为氢化钠。 其反应如下式所示：
Figure imgf000010_0001
具体实施过程如下： 冰浴下将丙二腈加入至氢化钠 ( 60%在油中）和乙二 醇二曱醚 (简称 DME)的悬浮液中， 恢复至室温， 搅拌 30分钟， 加入步骤 S03 获得的溴化产物和有机钯催化剂， 加热至回流 12小时后， 冷却至 0°C , 加入饱 和 Br2/H20溶液， 加入水， 抽滤， 水洗， 干燥， 硅胶柱层析分离得到产物。
在上述含杂环醌型噻。分有机光电材料的制备方法中， 化合物 A、 B、 C三种 单体的合成路线比较简单且成熟，从而减少工艺流程，降低制备成本。而且 Stille 耦合反应是一种成熟的耦合反应， 产率高、 条件温和， 易于控制， 且易通过引 入烷基或烷氧基， 提高产物的溶解性， 有利于扩大材料的加工性能。
本实施例的含杂环醌型噻。分有机光电材料可应用于各种光电或半导体器件 中， 例如， 可用于太阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、有机非线性材料和有机激光器件等。 下面以太阳能电池器件、 有机场效应晶体管、有机电致发光器件为例进行说明。其它如有机光存储器件， 有机非线性材料和有机激光器件与下面类似， 都是以本实施例的含杂环醌型噻 。分有机光电材料作为其的光存储材料、非线性材料、激光材料或半导体材料等。
请参阅图 3 , 显示采用上述实施例中含杂环醌型噻。分有机光电材料的太阳 能电池器件， 其包括依次层叠的玻璃基层 11、 透明阳极 12、 中间辅助层 13、 活性层 14、 阴极 15, 中间辅助层 13采用聚乙烯二氧基噻吩： 聚苯乙烯-磺酸复 合材料 (简称为 PEDOT:PSS ), 活性层 14包括电子给体材料和电子受体材料， 电子给体材料采用上述含杂环醌型噻吩有机光电材料， 电子受体材料可以是
[6,6]苯基 -C61 -丁酸曱酯 (简称为 PCBM )。 透明阳极 12可采用氧化铟锡 (简称 为 ITO ) , 优选为方块电阻为 10-20 Ω/ 的氧化铟锡。 阴极 15可采用铝电极。 其中， 玻璃基层 11可作为底层， 制作时， 先将 ITO电极沉积于玻璃基层 11 , 再用氧 -等离子喷涂（氧 -Plasma )处理工艺， 将中间辅助层 13形成于 ITO电极 上， 以及将含杂环醌型噻。分有机光电材料和电子受体材料通过真空蒸镀技术沉 积于中间辅助层 13上， 形成活性层 14, 然后再通过真空蒸镀技术在活性层 14 上沉积阴极 15, 获得上述太阳能电池器件。
如图所示， 在光照下， 光透过玻璃基层 11和 ITO电极 12, 活性层 14中的 含杂环醌型噻。分有机光电材料吸收光能， 并产生激子， 这些激子再迁移到电子 给体 /受体材料的界面处， 并将电子转移给电子受体材料， 如 PCBM, 实现电荷 的分离， 从而形成自由的载流子， 即自由的电子和空穴。 这些自由的电子沿电 子受体材料向金属阴极传递并被阴极所收集， 自由的空穴沿电子给体材料向 ITO 阳极传递并被阳极所收集， 从而形成光电流和光电压， 实现光电转换， 外 接负载 16时， 可对其进行供电。 在此过程中， 含杂环醌型噻。分有机光电材料由 于其具有艮宽的光语响应范围， 能够更充分地利用光能， 以获得更高的光电转 换效率， 增加太阳能电池器件的产电能力。 而且这种有机材料还能减轻太阳能 电池器件的质量， 并通过真空蒸镀等技术即可制作， 便于大批量的制备。
请参阅图 4, 显示采用上述实施例中的含杂环醌型噻。分有机光电材料的有 机电致发光器件， 其包括依次层叠设置的玻璃基层 21、 透明阳极 22、 发光层 23、 緩冲层 24、 阴极 25。 透明阳极 22可采用氧化铟锡（简称为 ITO ) , 优选 为方块电阻为 10-20 Ω/ 的氧化铟锡。 发光层 23包含上述实施例中的含杂环醌 型噻。分有机光电材料。 緩冲层 24可采用 LiF等， 但不限于此。 阴极 25可以是 但不限于金属 A1或 Ba等， 但不限于此。 因而， 在一个具体实施例中， 有机电 致发光器件结构表示为： ITO/含杂环醌型噻。分有机光电材料 /LiF/Al。 各层可采 用现有方法形成， 而含杂环醌型噻。分有机光电材料可通过真空蒸镀技术形成于 ITO上。
请参阅图 5 , 显示采用上述实施例中的含杂环醌型噻。分有机光电材料的有 机场效应晶体管， 其包括依次层叠设置的衬底 31、 绝缘层 32、 修饰层 33、 有 机半导体层 34以及设于有机半导体层 34上的源电极 35和漏电极 36。 其中， 衬底 31可以是但不限于高掺杂的硅片 （Si ) , 绝缘层 32可以是但不限于微纳 米（如 450 nm )厚的 Si02。 有机半导体层 34采用上述描述的含杂环醌型噻吩 有机光电材料。 源电极 35和漏电极 36均可采用但不限于金。修饰层 33可以是 但不限于十八烷基三氯硅烷。 衬底 31、 绝缘层 32、 修饰层 33 以及源电极 35 和漏电极 36都可采用现有的方法形成。 有机半导体层 34可以是在真空度接近 l(T4Pa下， 将上述实施例中的含杂环醌型噻。分有机光电材料蒸镀于由修饰层 33 修饰的绝缘层 32上。
以下通过具体实施例来举例说明含杂环醌型噻。分有机光电材料制备方法以 及其性能等方面。 以下各实施例用到的原料可采用现有的合成方法制备，例如， 下面的原料 4, 4，-二己基 -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻吩由 4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻吩与 1-溴己烷制得， 详细制备过程请参考文献： 《高分子》
( Macromolecules ) , 2007, 40, 1981 ); 4, 4，-双 (2-乙基-己基) -5, 5，-双 (三曱基硅) - 二噻吩 [3, 2-b: 2，， 3，-d]硅烷由 3, 3，-二溴 -5, 5，-双 (三曱基硅) -2, 2，-联二噻。分先后 与丁基锂和二氯二（2-乙基-己基) -硅烷制得， 详细制备过程请参考文献： 《美国 化学会志》 U Am. Chem. Soc. ) , 2008, 130, 16144 ); 2, 2，-联二噻吩由 2-溴噻吩 在 Ni(dppp)Cl2的催化作用下制得， 详细制备过程请参考文献： 《美国化学会志》
( J. Am. Chem. Soc. ) , 1997, 1 19, 12568 )。 实施例 1
本实施例 1的含杂环醌型噻。分有机光电材料结构如下所示：
Figure imgf000013_0001
由该结构式可知， 本实施例 1的含杂环醌型噻。分有机光电材料具有对称的 结构， 具有四个醌型噻。分环以及两对氛基， R2、 R5、 R6均为 H, R3、 R4均 为已基， a=b=l , 氛基作为吸电子基团， 通过此种均匀对称的结构， 使得含杂环 醌型噻。分有机光电材料相对具有较好的吸光性能和光电性能等，而且分子量小， 制成的产品质量较轻。
本实施例 1的含杂环醌型噻。分有机光电材料的制备方法具体过程如下： 1) 制备 4, 4，-二己基 -2, 6-二溴 -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻。分， 其结构式 如下所示：
Figure imgf000013_0002
其具体制备步骤为： 在冰浴、 避光条件下， 将 3.92 g NBS分批加入至盛有 3.47 g 4, 4，-二己基 -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻吩和 50 mL DMF的反应瓶中， 室温搅拌 12小时。 反应结束， 将反应液倒入冰水中淬灭， 乙酸乙酯萃取， 无水 硫酸钠干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 504.4 (M+)。
2) 制备 4, 4，-二己基 -2, 2，-双 (三曱基锡基 )-4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻 吩， 作为本实施例的化合物 C, 其结构式如下所示:
Figure imgf000014_0001
其具体制备步骤为： 在反应容器中加入 2.52 g 4, 4，-二己基 -2, 6-二溴 -4/ί-环 戊烷 [2, 1-b: 3, 4-b，]二噻吩和无水 40.0 mL THF溶液， 在 -25 °C下逐滴加入 4.13 mL正丁基锂溶液（2.9 M正己烷溶液） 。 搅拌 2小时后， 逐滴加入 2.38 g 三 曱基氯化锡， 继续搅拌 6小时。 反应完毕， 将反应液恢复到至室温， 加入饱和 氯化铵水溶液， 乙醚萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 672.2 (M+)。
3) 制备 4, 4，-二己基 -2, 6-双 (噻。分 -2-基) -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻吩， 其结构式如下所示：
Figure imgf000014_0002
在此步骤中， 即前述的步骤 S02, 由于化合物 A和 B结构相同（例如均为 2-溴噻。分)， 因此， 一方面可简化原料来源， 由此也简化了制备工艺和降低成本。 另一方面， 本步骤相对于采用不同化合物 A和 B时具有更高的产率。
具体制备过程为： 在氮气保护下， 将 25mL无水 THF加入至耐压管中， 快 速加入 2.02 g 4, 4，-二己基 -2, 2，-双 (三曱基锡基) -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻 吩和 1.08 g 2-溴噻吩，鼓泡 30分钟后加入 0.056 g Pd2(dba)3和 0.040 g P(o-Tol)3, 封盖， 升温至 80°C , 回流 26小时。 反应结束， 加入 15.0 mL KF (1.00 M) 水溶 液， 搅拌 30分钟， 加入饱和氯化钠水溶液， 乙酸乙酯萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 510.9 (M+)。
4) 制备 4, 4，-二己基 -2, 6-双 (5-溴 -噻吩 -2-基) -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻 吩， 其结构式如下所示：
Figure imgf000015_0001
具体制备过程为： 在冰浴、 避光条件下， 将 0.78 g NBS分批加入至盛有 1.02 g 4, 4，-二己基 -2, 6-双 (噻。分 -2-基) -4 /-环戊烷 [2, 1-b: 3, 4-b，]二噻吩和 20 mL DMF 的反应瓶中， 室温搅拌 12小时。 反应结束， 将反应液倒入冰水中淬灭， 三氯曱 烷萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 668.6 (M+)。
5) 最终产物的制备， 其结构式如上所示。
具体制备过程为： 冰浴下将 0.20 g 丙二腈加入至 0.24 g 氢化钠 （ 60%在油 中）和 20 mL 乙二醇二曱醚的悬浮液中， 恢复至室温，搅拌 30分钟，加入 0.72 g 2, 6-双 (5-溴-噻。分 -2-基)-二噻吩 [3,2-b,3'-d]并噻吩和 0.038 g PdCl2(PPh3)2o 加热 至回流 14小时后， 冷却至 0°C , 加入饱和 Br2/H20溶液。 加入水， 抽滤， 水洗， 干燥， 硅胶柱层析分离得到产物， 产率为 58 %。
测试结果为： MALDI-TOF-MS (m/z): 638.9 (M+)。 实施例 2
本实施例 2的含杂环醌型噻。分有机光电材料结构如下所示:
Figure imgf000016_0001
结构式与实施例 1的结构类似， 同样具有对称的结构， R2、 R5、 R6均 为 H, 不同在于 R3、 R4为 2-乙基-己基， X为 Si, 且具有六个醌型噻吩环， 即 a=b=2, 氛基作为吸电子基团， 通过此种均匀对称的结构， 使得含杂环醌型噻吩 有机光电材料相对具有较好的吸光性能和光电性能等。
本实施例的含杂环醌型噻。分有机光电材料的制备方法具体过程如下： 1) 制备 5-溴 -2, 2'-联二噻吩， 作为本实施例的化合物 A和 B, 其结构式如 下所示：
Figure imgf000016_0002
由于化合物 A和 B结构相同， 由此只需要进行一次步骤 2 ) 即可制备出化 合物 A和 B, 简化了制备工艺和降低成本。 相反， 如果含杂环醌型噻。分有机光 电材料不是对称的结构， 那么化合物 A和 B结构不同， 则需要对不同的原料分 别进行步骤 2 )。
其具体制备步骤为： 在冰浴、 避光条件下， 将 17.80 g NBS分批加入至盛 有 16.60 g 2, 2，-联二噻吩和 200 mL DMF的反应瓶中 , 室温搅拌 12小时。 反应 结束， 将反应液倒入冰水中淬灭， 三氯曱烷萃取， 无水硫酸镁干燥， 旋蒸， 硅 胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 245.2 (M+)。
2) 制备 4, 4，-双 (2-乙基-己基) -5, 5，-二溴-二噻吩 [3, 2-b:2', 3，-d]硅烷，其结构 式如下所示：
Figure imgf000017_0001
其具体制备步骤为： 将 16.90 g 4, 4，-双 (2-乙基-己基) -5, 5，-双 (三曱基硅) -二 噻。分 [3, 2-b: 2，， 3，-d]硅烷溶解在 200 mL 四氢呋喃中， 分批加入 11.00 g NBS, 室 温搅拌 6小时。 反应结束， 乙醚萃取， 无水硫酸钠干燥， 抽滤， 旋蒸， 硅胶柱层 析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 576.6 (M+)。
3) 制备 4, 4，-双 (2-乙基-己基) -5, 5，-双 (三曱基锡) -二噻吩 [3, 2-b:2', 3，-d]硅 烷， 作为本实施例的化合物 C, 其结构式如下所示：
Figure imgf000017_0002
其具体制备步骤为：加入 11.52 g 4, 4，-双 (2-乙基-己基) -5, 5，-二溴-二噻吩 [3, 2-b:2，， 3，-d]硅烷和无水 100.0 mL THF溶液， 在 -25 °C下逐滴加入 17.8 mL正丁 基锂溶液（2.7 M正己烷溶液） 。 搅拌 2小时后， 逐滴加入 9.71 g三曱基氯化 锡， 继续搅拌 6小时。 反应完毕， 将反应液恢复到至室温， 加入饱和氯化铵水 溶液， 乙醚萃取， 无水硫酸镁干燥， 旋蒸。 此步骤结束后可不需要提纯， 直接 做下一步。
测试结果为： MALDI-TOF-MS (m/z): 744.4 (M+)。
4) 制备 2, 6-双 (2, 2，-联二噻。分 -5-基)- 4, 4，-双 (2-乙基-己基)-二噻吩 [3, 2-b:2' 3，-d]硅烷， 其结构式如下所示：
Figure imgf000018_0001
同实施例 1 , 由于化合物 A和 B结构相同， 因此，一方面可简化原料来源 , 由此也简化了制备工艺和降低成本。 另一方面， 本步骤相对于采用不同化合物 A和 B时具有更高的产率。
具体制备过程为： 在氮气保护下， 将 80mL无水 THF加入至耐压管中， 快 速加入 7.44 g 4, 4，-双 (2-乙基-己基) -5, 5，-双 (三曱基锡) -二噻吩 [3, 2-b:2', 3，-d]硅 烷和 5.40 g 5-溴 -2, 2，-联二噻。分， 鼓泡 30分钟后加入 0.19 g Pd2(dba)3和 0.14 g P(o-Tol)3,封盖， 升温至 80°C , 回流 24小时。反应结束，加入 30.0 mL KF (1.00 M) 溶液， 搅拌 40分钟， 加入饱和氯化钠水溶液， 乙醚萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z): 747.3 (M+)。
5) 制备 2, 6-双 (5，-溴 -2, 2，-联二噻。分 -5-基)- 4, 4，-双 (2-乙基-己基)-二噻吩 [3, 2-b:2，，3，-d]硅烷， 其结构式如下所示：
Figure imgf000019_0001
具体制备过程为： 在冰浴、 避光条件下， 将 3.91 g NBS分批加入至盛有 3.74 g 2, 6-双 (2, 2，-联二噻吩 -5-基)- 4, 4，-双 (2-乙基-己基) -二噻吩 [3, 2-b:2', 3，-d]硅烷 和 50 mL DMF的反应瓶中， 室温搅拌 12小时。反应结束， 将反应液倒入冰水中， 三氯曱烷萃取， 无水硫酸镁干燥， 旋蒸， 硅胶柱层析分离得到产物。
测试结果为： MALDI-TOF-MS (m/z)： 905.1 (M+)。
6) 最终产物的制备， 其结构式如上所示。
具体制备过程为： 冰浴下将 0.16 g 丙二腈加入至 0.20 g 氢化钠 （60%在油 中）和 30 mL 乙二醇二曱醚的悬浮液中， 恢复至室温，搅拌 40分钟，加入 1.81 g 2, 6-双 (5，-溴 -2, 2，-联二噻吩 -5-基)- 4, 4，-双 (2-乙基-己基)-二噻吩 [3, 2-b:2', 3'-d] 硅烷和 0.070 g PdCl2(PPh3)2。 加热至回流 12小时后， 冷却至 0°C , 加入饱和 Br2/H20 溶液。 加入水， 抽滤， 水洗， 干燥， 硅胶柱层析分离得到产物， 产率 为 61%。
测试结果为： MALDI-TOF-MS (m/z): 873.4 (M+)。
由上可知， 上述含杂环醌型噻。分有机光电材料中， 其具有多个醌型噻吩环 结构， 由于噻吩环是五元环结构， 符合休克儿规则， 具有适中的能带隙， 较宽 的光语响应， 较好的热稳定性和环境稳定性。 而且， 上述含杂环醌型噻。分有机 光电材料在分子的两端引入强吸电子基团二氛基乙婦基（ = C(CN)2 ),成为含二 噻吩并噻吩单元的醌型噻吩结构， 扩大了共轭结构， 增加了分子的平面性， 有 利于降低材料的能隙， 从而进一步加宽材料对太阳光语的吸收范围， 例如可将 材料的吸收带边沿推向红光及近红外区， 从而提高材料的光电性能和光电转换 效率。 在上述含杂环醌型噻。分有机光电材料制备方法中， 采用较简单的合成路 线和 Stille耦合反应， 可简化工艺和降低制备成本。 上述含杂环醌型噻。分有机 光电材料应用于太阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有 机光存储器件、 有机非线性材料或有机激光器件中时， 可提高其光电或半导体 相关性能， 并能减轻器件的质量， 且便于大批量的制备。
以上所述仅为本发明的较佳实施例而已， 并不用以限制本发明， 凡在本发 明的精神和原则之内所作的任何修改、 等同替换和改进等， 均应包含在本发明 的保护范围之内。

Claims

权 利 要 求 书 种含杂环醌型噻。分有机光电材料， 其包含如下结构式（1 )表示的化
Figure imgf000021_0001
式中： 、 R2、 R5、 R6是相同或不同地表示为 11或 d-C^的烷基或烷氧基， R3、 是相同或不同地表示为 CrC2。的烷基或烷氧基， a、 b是相同或不同地表 示为 1-12之间的整数； X为 81或 。
2、 如权利要求 1所述的含杂环醌型噻。分有机光电材料， 其特征在于， 所述 、 R6为相同的 11、 C C20烷基或烷氧基, 所述 R2、 R5为相同的 11、 CrC2。烷 基或烷氧基， 所述 R3、 R4是相同 d-C^的烷基或烷氧基。
3、 如权利要求 1所述的含杂环醌型噻。分有机光电材料， 其特征在于， 所述 a、 b是相同的 1-12之间的整数。
4、 如权利要求 1所述的含杂环醌型噻。分有机光电材料， 其特征在于， 所述 a、 b均为 1或 2。
5、 一种含杂环醌型噻。分有机光电材料制备方法， 其包括如下步骤： 分别提供如下结构式表示的化合物 A、 B、 C以及丙二腈，
Figure imgf000021_0002
同地表示为 H或 C C20的烷基或烷氧基， R3、 R4是相同或不同地表示为 -C: 的烷基或烷氧基； a、 b是相同或不同地表示为 1-12之间的整数； X为 Si或 C,
An为 d-C4的烷基；
在催化剂和溶剂的条件下， 将化合物 、 B、 C进行 Stille耦合反应； 将 Stille耦合反应产物进行溴化取代反应， 生成溴化产物；
在催化剂、 缩合剂和溶剂的条件下， 将溴化产物与丙二腈进行缩合反应， 获得如下结构式 ( 1 )表示的化合物：
Figure imgf000022_0001
6、如权利要求 5所述的含杂环醌型噻。分有机光电材料制备方法，其特征在 于， 在进行 Stille耦合反应、 溴化取代反应和缩合反应后， 分别进一步用硅胶 柱层析分离提纯， 得到对应的耦合反应产物、 溴化产物和结构式 (1)表示的化合 物。
7、如权利要求 5所述的含杂环醌型噻。分有机光电材料制备方法，其特征在 于， 所述溴化取代反应是在二曱基曱酰胺、 四氢呋喃、 四氯化碳、 氯仿、 二氯 曱烷或乙腈作为溶剂的条件下， 将 Stille耦合反应产物与 N-溴代丁二酰亚胺、 Br2、 HBr或 PBr3进行的取代反应。
8、如权利要求 5所述的含杂环醌型噻。分有机光电材料制备方法，其特征在 于， 所述缩合反应采用的催化剂为有机钯催化剂，采用的溶剂为乙二醇二曱醚、 乙醇、 曱醇、 二氯曱烷、 三氯曱烷、 四氢呋喃、 乙酸乙酯、 DMF、 曱苯或丙酮。
9、如权利要求 5所述的含杂环醌型噻。分有机光电材料制备方法，其特征在 于， 所述 Stille耦合反应采用的催化剂为有机钯催化剂， 溶剂为四氢呋喃、 二 氯曱烷、 乙二醇二曱醚、 苯或曱苯， 缩合剂为氢化钠或醇钠。
10、 如权利要求 1-4任一项所述的含杂环醌型噻。分有机光电材料在制备太 阳能电池器件、 有机场效应晶体管、 有机电致发光器件、 有机光存储器件、 有 机非线性材料或有机激光器件中的应用。
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