阅读说明：本技术 一种含4-乙烯基吡啶合镉的聚合配合物及其制备方法与用途 (Polymeric complex containing 4-vinylpyridine cadmium and preparation method and application thereof ) 是由 钟超凡 唐时雨 陈旭 闻高峰 徐泽化 王凯旋 于 2018-06-14 设计创作，主要内容包括：本发明涉及一种以4-乙烯基吡啶合镉配合物作辅助电子受体A的D-A-π-A型聚合配合物(如下式)及其制备方法,其用途为在染料敏化太阳能电池中作染料敏化剂,该聚合配合物是以大π共轭结构的苯并二噻吩联二噻吩衍生物(BDTT)为电子给体D,以4-乙烯基吡啶合镉配合物作辅助电子受体A,以与镉配位的另一个配体8-羟基喹啉作π桥,氰基丙烯酸为电子受体A和锚定基团,将镉配合物与给体BDTT通过Heck聚合反应制备的一种新型聚合配合物染料敏化剂PBDTT-PY-Cd,该染料敏化剂表现出良好的光伏性能和高的热稳定性,其光电转化效率PCE达到8.01%,热分解温度为301℃,对染料敏化太阳能电池的研发具有一定的应用价值。<Image he="354" wi="393" file="DEST_PATH_IMAGE001.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a D-A-pi-A type polymeric complex (as shown in the following formula) taking a 4-vinylpyridine cadmium complex as an auxiliary electron acceptor A and a preparation method thereof, wherein the polymeric complex is used as a dye sensitizer in a dye-sensitized solar cell, the polymeric complex takes a benzodithiophene Bithiophene Derivative (BDTT) with a large pi conjugated structure as an electron donor D, the 4-vinylpyridine cadmium complex as the auxiliary electron acceptor A, another ligand 8-hydroxyquinoline coordinated with cadmium as a pi bridge, cyanoacrylate as an electron acceptor A and an anchoring group, the cadmium complex and the BDTT are subjected to Heck polymerization to prepare a novel polymeric complex dye sensitizer PBDTT-PY-Cd, the dye sensitizer has good photovoltaic performance and high thermal stability, and the photoelectric conversion efficiency reaches 8.01 percent, the thermal decomposition temperature is 301 ℃, and the method has certain application value for the research and development of dye-sensitized solar cells.)

1. A polymeric complex PBDTT-PY-Cd containing 4-vinylpyridinium cadmium is characterized in that the compound has a D-A-Pi-A structure containing 4-vinylpyridinium cadmium complex as an electron auxiliary receptor A, and the general formula is as follows:

formula 1 is a structural general formula of a 4-vinylpyridine cadmium-containing polymeric complex PBDTT-PY-Cd.

2. The preparation method of the 4-vinylpyridinium-cadmium containing polymeric complex PBDTT-PY-Cd as claimed in claim 1:

(1) 4-vinylpyridine (1) is synthesized by adding 4-methylpyridine, paraformaldehyde, benzoic acid and distilled water in a molar ratio of 0.040:0.080:0.005:1.000 into a three-neck reaction bottle, heating and refluxing for 10 ~ 20 h under normal pressure, evaporating a small amount of unreacted 4-methylpyridine under reduced pressure to obtain crude pyridylethanol, putting a proper amount of sodium hydroxide aqueous solution into a three-neck reaction bottle, adding a small amount of methylene blue, heating to 130 ~ 150 ℃, dropwise adding the crude pyridylethanol under reduced pressure, immediately distilling the vinylpyridine and water, rapidly cooling to room temperature, simultaneously adding the methylene blue and a small amount of solid sodium hydroxide, standing for 24 ~ 36 h to obtain a solution which is divided into two layers, adding the vinylpyridine as an upper layer, and performing reduced pressure distillation at a temperature of the methylene blue of below 50 ℃ to obtain a colorless liquid, wherein the boiling point is 120 ~ 121 ℃, adding the methylene blue into pure 4-vinylpyridine for preservation so as to prevent polymerization;

(2) synthesis of cadmium-containing complex (PY-Cd) (2): dissolving an auxiliary ligand 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid and a ligand 4-vinylpyridine in a molar ratio of 1:1 in a proper amount of tetrahydrofuran solution, and slowly dropwise adding a certain amount of cadmium acetate (Cd (CH)₃COO)₂·2H₂Adding dropwise a methanol solution of O), measuring the pH value of the system, adjusting by using glacial acetic acid or ammonia water if necessary to keep the system in weak acidity, only heating the system to 50 ~ 60 ℃ because the stability of the ligand 4-vinylpyridine is limited, continuing to react for 6 ~ 10 h, stopping the reaction, cooling the obtained mixture to room temperature, filtering, washing the filtered solid by using absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain a yellow solid product;

(3) synthesis of polymeric Metal Complex (PBDTT-PY-Cd) (3): the polymeric metal complex PBDTT-PY-Cd is obtained by Heck polymerization, and the complex monomer PY-Cd and the donor monomer 2, 6-dibromo-4, 8-di (5- (2-ethyl octyl) thiophene-2-yl) benzo [1,2-b:4,5-b ] are sequentially weighed according to the molar ratio of 1.000:1.000:0.041: 0.229']Dithiophene (BDTT), and palladium acetate (Pd (CH) as catalyst₃COO)₂And tri (2-tolyl) phosphine, adding refined DMF solvent and a small amount of dried triethylamine, heating to 90 ~ 100 ℃ under the protection of nitrogen, continuing to react for 48 ~ 72 h, standing the system to room temperature after the reaction is stopped, filtering the solid in the mixture, washing the solid with anhydrous methanol for several times, and drying in vacuum to obtain a brown yellow solid product.

3. The use of the polymeric complex PBDTT-PY-Cd containing 4-vinylpyridinium cadmium as claimed in claim 1 as a dye sensitizer in dye-sensitized solar cells.

Technical Field

The invention relates to a D-A-pi-A type polymeric complex taking a 4-vinylpyridine cadmium complex as an auxiliary electron acceptor A and a preparation method thereof, and belongs to the field of photoelectric materials in new materials, wherein the D-A-pi-A type polymeric complex is applied to a dye-sensitized solar cell as a dye sensitizer.

Background

Dye-sensitized solar cells (DSSC), one of the most promising organic solar cells for research and development applications at present, have attracted intensive research worldwide, the dye sensitizer can generate photo-generated electrons after absorbing sunlight and is a key photosensitive material of a dye-sensitized solar cell (DSSC), and the synthesis and performance research of the dye sensitizer is started from ruthenium-based complex dye, however, the research of pure organic and common transition metal complex dye sensitizers is gradually turned to due to the high cost and limited sources of ruthenium, the existing organic dye sensitizers have the defects of poor stability, limited photoelectric efficiency and the like, the light absorption performance of common metal complexes is limited, and in order to solve the problems, the invention researches a polymerization complex dye sensitizer obtained by polymerizing organic and complex dyes, and the light absorption performance, the electron transmission performance and the photoelectric conversion efficiency of the polymerization complex dye sensitizer are improved. Disclosure of Invention

The purpose of the invention is as follows: in particular to a D-A-pi-A type polymeric complex dye sensitizer PBDTT-PY-Cd with a 4-vinylpyridine cadmium complex as an auxiliary electron acceptor and a preparation method thereof. The electron acceptor part 4-vinylpyridine cadmium complex and the electron donor part dithiophene-Benzodithiophene Derivative (BDTT) are polymerized through Heck polymerization reaction to form the polymerization complex functional dye with a D-A-pi-A structure, and the polymerization complex functional dye is applied to a dye-sensitized solar cell and is used as a dye sensitizer.

The technical scheme of the invention is as follows: a polymeric complex containing 4-vinylpyridinium cadmium is characterized in that the compound takes 4-vinylpyridinium cadmium complex as an auxiliary electron acceptor A, has a D-A-pi-A type molecular structure, and has a general formula as shown in formula 1:

formula 1 is a structural general formula of a polymerization complex PBDTT-PY-Cd containing 4-vinylpyridine cadmium.

A preparation method of a polymerization complex PBDTT-PY-Cd containing 4-vinylpyridine cadmium comprises the following steps:

(1) the synthesis of 4-vinylpyridine (1) comprises adding 4-methylpyridine, paraformaldehyde, benzoic acid and distilled water in a molar ratio of 0.040:0.080:0.005:1.000 into a three-neck reaction flask, heating and refluxing for 10 ~ 20 h under normal pressure, distilling off unreacted 4-methylpyridine under reduced pressure to obtain crude pyridylethanol, putting a proper amount of sodium hydroxide aqueous solution into the three-neck reaction flask, adding a small amount of methylene blue, heating to 130 ~ 150 ℃, dropwise adding crude pyridylethanol under reduced pressure, immediately distilling the vinylpyridine and water, rapidly cooling to room temperature, simultaneously adding the methylene blue and a small amount of solid sodium hydroxide, standing for 24 ~ 36 h to separate the solution into two layers, adding the vinylpyridine as an upper layer, and performing reduced pressure distillation at a temperature of the methylene blue of below 50 ℃ to obtain colorless liquid, wherein the boiling point is 120 ~ 121 ℃, adding the methylene blue into pure 4-vinylpyridine for preservation to prevent polymerization;

(2) synthesis of cadmium-containing complex (PY-Cd) (2): dissolving an auxiliary ligand 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid and a ligand 4-vinylpyridine in a molar ratio of 1:1 in a proper amount of tetrahydrofuran solution, and slowly dropwise adding a certain amount of cadmium acetate (Cd (CH)₃COO)₂·2H₂Measuring the pH value of the system after dropwise adding the methanol solution of O), adjusting by using glacial acetic acid or ammonia water if necessary to keep the pH value of the system to be weakly acidic, only heating the system to 50 ~ 60 ℃ because the stability of the ligand 4-vinylpyridine is limited, continuing to react for 6 ~ 10 h, stopping the reaction, cooling the obtained mixture to room temperature, filtering, washing the filtered solid by using absolute ethyl alcohol, and drying the product in a vacuum drying oven to obtain a yellow solid product;

(3) synthesis of polymeric Metal Complex (PBDTT-PY-Cd) (3): the polymeric metal complex PBDTT-PY-Cd is obtained by Heck polymerization, and the complex monomer PY-Cd and the donor monomer 2, 6-dibromo-4, 8-di (5- (2-ethyl octyl) thiophene-2-yl) benzo [1,2-b:4,5-b ] are sequentially weighed according to the molar ratio of 1.000:1.000:0.041: 0.229']Dithiophene (BDTT), and palladium acetate (Pd (CH) as catalyst₃COO)₂And tri (2-tolyl) phosphine, followed by addition of refined DMF solvent, and a small amount of dried triethyleneamineHeating to 90 ~ 100 ℃ under the protection of amine and nitrogen, continuing to react for 48 ~ 72 h, standing the system to room temperature after the reaction is stopped, filtering the solid in the mixture, washing the solid with anhydrous methanol for a plurality of times, and drying the solid in vacuum to obtain a brown yellow solid product;

use of a polymeric complex containing cadmium 4-vinylpyridinium: is used as a dye sensitizer in a dye-sensitized solar cell.

The invention has the main advantages that: a polymerization complex containing 4-vinylpyridine cadmium takes the complex of 4-vinylpyridine cadmium as an auxiliary electron acceptor, and an organic metal complex is polymerized to enlarge a conjugated pi system of a complex molecule and improve the light absorption performance and the carrier transmission capacity of the complex, thereby improving the photovoltaic performance of the complex as a dye sensitizer.

Drawings

FIG. 1 NMR spectra of 4-vinylpyridine synthesized in example of the present invention: (¹HNMR)（400MHz，CDCl₃，TMS）；

FIG. 2 Infrared Spectroscopy (IR) of PY-Cd and PBDTT-PY-Cd Compounds synthesized in the examples of the invention (KBr Crystal pellets, 4000 ~ 500 cm^-1）；

FIG. 3 is an ultraviolet-visible absorption spectrum (UV-vis) of the compounds PY-Cd and PBDTT-PY-Cd synthesized by the example of the present invention;

FIG. 4 thermogravimetric analysis (TGA) curve (TGA) of PBDTT-PY-Cd, a compound synthesized by an example of the present invention;

FIG. 5 is a current density-voltage (J-V) curve of a dye-sensitized solar cell using PBDTT-PY-Cd as a dye sensitizer synthesized in an example of the present invention;

FIG. 6 is a graph showing external quantum efficiency (IPCE) curves of dye-sensitized solar cells using PBDTT-PY-Cd as a dye sensitizer synthesized in the example of the present invention.

Detailed Description

The preparation and synthesis reaction route of the compound of the invention is as follows:

the present invention will be further described with reference to the following specific examples.