阅读说明：本技术 一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物及其制备方法与用途 (Polymeric complex containing 4-vinylaniline derivative and Zn (II) and preparation method and application thereof ) 是由 钟超凡 王凯旋 陈天祺 闻高峰 徐泽化 唐时雨 于 2018-06-14 设计创作，主要内容包括：本发明涉及一种以4-乙烯基苯胺与锌(II)离子形成的配体作为辅助受体A的D-A-π-A型聚合配合物(如下式)的发明及制备方法,其用途为用于染料敏化太阳能电池中作染料敏化剂。该聚合配合物以二噻吩-苯并二噻吩衍生物(BDTT)为给体(D),以4-乙烯基苯胺与锌(II)离子形成的配体作为辅助受体(A),以8-羟基喹啉作为π桥,以氰基丙烯酸为电子受体(A)和锚定基团,将Zn(II)配合物与二噻吩-苯并二噻吩衍生物通过Heck聚合反应而制备得到的一种新型聚合配合物PBDTT-VZn,该聚合配合物表现出良好的光电转化等光伏性能和高的热稳定性,光电转化效率达到7.61%,热分解温度达315℃,这将在染料敏化太阳能电池的开发应用方面具有一定的前景。<Image he="346" wi="408" file="326725DEST_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 ligand formed by 4-vinylaniline and zinc (II) ions as an auxiliary receptor A and a preparation method thereof, and the application of the polymeric complex is used as a dye sensitizer in a dye-sensitized solar cell. The polymerization complex takes a dithiophene-Benzodithiophene Derivative (BDTT) as a donor (D), a ligand formed by 4-vinylaniline and zinc (II) ions as an auxiliary receptor (A), 8-hydroxyquinoline as a pi bridge, cyanoacrylate as an electron receptor (A) and an anchoring group, and a Zn (II) complex and the dithiophene-benzodithiophene derivative are subjected to Heck polymerization reaction to prepare a novel polymerization complex PBDTT-VZn, wherein the polymerization complex shows good photovoltaic performance such as photoelectric conversion and the like, high thermal stability and photoelectric conversion efficiencyThe thermal decomposition temperature reaches 315 ℃ and reaches 7.61 percent, which has certain prospect in the development and application of dye-sensitized solar cells.)

1. A polymeric complex PBDTT-VZn containing 4-vinylaniline derivatives and Zn (II) is characterized in that the compound has a D-A-pi-A structure containing the 4-vinylaniline derivatives and Zn (II) complexes as electron auxiliary acceptors A, and the general formula is as shown in formula 1:

formula 1 the general structural formula of a polymeric complex PBDTT-VZn containing 4-vinylaniline derivatives and Zn (II).

2. The process according to claim 1 for preparing a polymeric complex PBDTT-VZn containing 4-vinylaniline derivative and Zn (II):

(1) preparation of p-nitrobenzyl triphenyl phosphonium bromide: adding 4-benzyl bromomethyl nitrobenzene and triphenyl phosphine to CHCl under inert condition₃After stirring for 0.5 ~ 1.0.0 h, pouring the mixture into anhydrous ether, separating out a white solid, filtering, taking a precipitate, and drying in an oven to obtain a white powder solid p-nitrobenzyl triphenyl phosphonium bromide;

(2) preparation of p-nitroanisole: p-nitrobenzyl triphenyl phosphonium bromide and formaldehyde suspension are stirred vigorously, and Na is added₂CO₃ Dissolving in water, adding Na after the intermediate of deep red phosphorus salt disappears₂CO₃After the solution is added, continuously stirring for 4 ~ 8 h, extracting with diethyl ether, removing the diethyl ether by spinning, and then passing through a silica gel column by using petroleum ether as an eluent to obtain light yellow liquid p-nitrostyrene;

(3) the preparation of p-4-aminostyrene comprises the steps of dissolving p-nitrostyrene in dry dioxane, adding water, stirring for 10 min, adding Zn powder, heating to 70 ℃, reacting for 7 ~ 8 h, decompressing after the reaction is finished, removing the solvent, extracting a water layer by using ethyl acetate, enabling an organic layer to be a crude product, passing through a silica gel column, and obtaining light yellow solid p-4-aminostyrene, wherein the eluent is petroleum ether and ethyl acetate = 5: 1;

(4) synthesis of zn (ii) -containing complex (VZn): respectively weighing 4-aminostyrene and 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid, adding the 4-aminostyrene and the 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid into a three-neck round-bottom flask containing tetrahydrofuran successively after weighing, stirring, and continuously dissolving Zn (CH)₃COO)₂·H₂Slowly dripping the methanol solution of O into the reaction system through a constant-pressure dropping funnel, heating to reflux reaction for 12 ~ 24 h after dripping is finished, cooling the system to room temperature after the reaction is finished, filtering precipitated solid, andwashing with deionized water and absolute ethyl alcohol for 2 times, recrystallizing the crude product with absolute methyl alcohol for two times, and drying under vacuum for several days to obtain a brown yellow solid VZn;

(5) preparation of polymeric Metal Complex (PBDTT-VZn) the polymer (PBDTT-VZn) was synthesized according to the Heck coupling reaction, Zn (II) complex VZn, 2, 6-dibromo-4, 8-bis (5- (2-ethylhexyl) thienyl-2-yl) -benzo [1,2-b:4,5-b' ] dithiophene (BDTT) was added to a single vial, then palladium acetate, tri (o-tolyl) phosphine were added, freshly distilled, refined and dried DMF solution and triethylamine were added in sequence to the single vial, then the temperature was raised to 90 ℃ under nitrogen atmosphere for reaction 36 ~ 72h, the system was filtered after the reaction was finished and cooled to room temperature, the obtained residue was washed with a large amount of methanol to finally obtain brown precipitate PBDTT-VZn.

3. Use of the polymeric complex PBDTT-VZn containing 4-vinylaniline derivative and zn (ii) according to claim 1 as a dye sensitizer in dye-sensitized solar cells.

Technical Field

The invention relates to a D-A-pi-A type polymerization complex dye taking 4-vinylaniline derivatives and Zn (II) as an auxiliary electron acceptor A, a preparation method thereof and a dye sensitizer used in a dye-sensitized solar cell, belonging to the field of photoelectric materials in new materials.

Background

The dye-sensitized solar cell is invented by Gr ä tzel and O' Regan in 1991, and the photovoltaic principle is that under illumination, a thin film TiO film is adsorbed on a FTO glass polar plate of the cell₂The dye sensitizer molecules on the surface of the particles absorb light and change from a ground state to an excited state due to the excited state of the dye and the TiO₂Difference in energy level of conduction band, injection of excited electrons into TiO₂Conduction band, electron passing sensitized TiO₂After the film is transferred to the FTO glass electrode, electrons are transmitted to a counter (positive) electrode of the cell through an external circuit, then the redox electrolyte in the cell is transferred to an excited state of a dye sensitizer molecule, so that the dye sensitizer molecule returns to a ground state, and electrons lost by the redox electrolyte are supplemented by the electrons injected into the counter electrode, so that a whole photoproduction electron circulation loop is formed.

The dye sensitizer is the most critical component of the dye-sensitized solar cell and plays a role in absorbing sunlight to generate electrons, and the electrons pass through TiO₂The close combination of the two components can effectively transfer electrons and the like. Research has shown that metal complexes and polymeric metal complexes are the most potential dyes, and the structures thereof are D-A type, D-pi-A type, D-A-pi-A type and the like. The configuration of the combination of the donor (D) and the acceptor (A), namely D-A type, is a dye sensitizer configuration which is relatively studied earlier, and with continuous and intensive research on the sensitizer, it is found that the introduction of a pi bridge between D and A can facilitate the transfer of electrons between D and A and obtain better spectral absorption. In recent years, a novel high-efficiency stable D-A-pi-A type dye sensitizer is provided, and an auxiliary electron acceptor A is added on the basis of the D-pi-A type dye sensitizer to enhance light absorption, reduce charge recombination and strengthen electron transfer, so that the photoelectric conversion efficiency and the photovoltaic performance of a battery can be improved. The idea of using 4-vinylaniline derivatives and Zn (II) as auxiliary electron-withdrawing groups is based onThe idea is as follows: firstly, transition metal in the adopted complex has an empty orbit, so that a ligand has adjustable electron-withdrawing capability; secondly, the four coordination adopted by the metal ligand adopted by the sensitizer has good planarity, which is beneficial to good conjugation of sensitizer molecules, is beneficial to electron transmission in molecules, and is beneficial to improving the photoelectric conversion efficiency of the dye and prolonging the service life. Therefore, the invention researches and develops a D-A-pi-A type polymeric metal complex which takes a 4-vinylaniline derivative and Zn (II) complex as an auxiliary electron acceptor A and is used as a dye sensitizer of a dye-sensitized solar cell.

Disclosure of Invention

The purpose of the invention is as follows: which provides a dye sensitizer PBDTT-VZn of a D-A-pi-A type polymerization complex taking a 4-vinylaniline derivative and Zn (II) complex as an auxiliary electron acceptor and a preparation method thereof. 4-vinylaniline derivatives Zn (II) complex electron acceptor parts and dithiophene-Benzodithiophene Derivatives (BDTT) donor parts 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 dye-sensitized solar cells and used as a dye sensitizer.

The technical scheme of the invention is as follows: a polymeric complex containing a 4-vinylaniline derivative and Zn (II). The compound is characterized in that 4-vinylaniline derivative and Zn (II) complex are used as an auxiliary electron acceptor A, and the compound has a D-A-pi-A type molecular structure, and the general formula of the compound is as shown in formula 1:

formula 1 is a general structural formula of polymeric compound PBDTT-VZn containing 4-vinylaniline derivatives and Zn (II).

A preparation method of poly-PBDTT-VZn containing 4-vinylaniline derivatives and Zn (II) comprises the following steps:

(1) preparation of p-nitrobenzyl triphenyl phosphonium bromide: adding 4-benzyl bromomethyl nitrobenzene and triphenyl phosphine to CHCl under inert condition₃ Stirring for 0.5 ~ 1.0.0 h, pouring the mixture into anhydrous ether, separating out white solid, filtering,drying the precipitate in an oven to obtain white powder solid p-nitrobenzyl triphenyl phosphonium bromide;

(2) preparation of p-nitroanisole: p-nitrobenzyl triphenyl phosphonium bromide and formaldehyde suspension are stirred vigorously, and Na is added₂CO₃Dissolving in water, adding Na after the intermediate of deep red phosphorus salt disappears₂CO₃After the solution is added, continuously stirring for 4 ~ 8 h, extracting with diethyl ether, removing the diethyl ether by spinning, and then passing through a silica gel column by using petroleum ether as an eluent to obtain light yellow liquid p-nitrostyrene;

(3) dissolving p-nitrostyrene in dry dioxane, adding water, stirring for 10 min, adding Zn powder, heating to 70 ℃, reacting for 7 ~ 8 h, decompressing after the reaction is finished, removing the solvent, extracting an aqueous layer by using ethyl acetate, enabling an organic layer to be a crude product, passing through a silica gel column, and obtaining pale yellow solid p-4-aminostyrene, wherein the eluant is petroleum ether and ethyl acetate = 5: 1;

(4) synthesis of zn (ii) -containing complex (VZn): respectively weighing 4-aminostyrene and 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid, adding the 4-aminostyrene and the 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid into a three-neck round-bottom flask containing tetrahydrofuran successively after weighing, stirring, and continuously dissolving Zn (CH)₃COO)₂·H₂Slowly dropwise adding the methanol solution of O into a reaction system through a constant-pressure dropping funnel, heating to reflux reaction for 12 ~ 24 h after dropwise adding is finished, cooling the system to room temperature after the reaction is finished, filtering precipitated solids, washing with deionized water and absolute ethyl alcohol for 2 times, recrystallizing the crude product with absolute methanol for two times, and drying for several days under a vacuum condition to obtain a brown yellow solid VZn;

(5) preparation of polymeric Metal Complex (PBDTT-VZn) the polymer (PBDTT-VZn) was synthesized according to the Heck coupling reaction, Zn (II) complex VZn, 2, 6-dibromo-4, 8-bis (5- (2-ethylhexyl) thienyl-2-yl) -benzo [1,2-b:4,5-b' ] dithiophene (BDTT) was added to a single vial, then palladium acetate, tri (o-tolyl) phosphine were added, freshly distilled, refined and dried DMF solution and triethylamine were added in sequence to the single vial, then the temperature was raised to 90 ℃ under nitrogen atmosphere for reaction 36 ~ 72h, the system was filtered after the reaction was finished and cooled to room temperature, the obtained residue was washed with a large amount of methanol to finally obtain brown precipitate PBDTT-VZn.

Use of a polymeric complex PBDTT-VZn containing 4-vinylaniline derivatives and zn (ii): is used as a dye sensitizer in a dye-sensitized solar cell.

The invention has the main advantages that: a polymeric complex containing 4-vinylaniline derivative and Zn (II) takes the 4-vinylaniline derivative and Zn (II) complex as an auxiliary electron acceptor, and polymerizes an organic metal complex to enlarge a conjugated pi system of the complex molecule and improve the light absorption performance and the carrier transmission capability of the complex molecule, thereby improving the photovoltaic performance of the complex as a dye sensitizer.

Drawings

FIG. 1 NMR spectrum of p-4-aminostyrene synthesized by the example of the present invention: (¹HNMR)（400MHz，CDCl₃，TMS）；

FIG. 2 Infrared Spectroscopy (IR) of VZn, PBDTT-VZn compound synthesized in the example of the invention (KBr Crystal pellet, 4000 ~ 450 cm^-1）；

FIG. 3 is a thermogravimetric analysis (TGA) curve of a polymeric metal complex PBDTT-VZn synthesized by an example of the present invention;

FIG. 4 is an ultraviolet-visible absorption spectrum (UV-vis) of a polymeric metal complex PBDTT-VZn 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 a polymeric metal complex PBDTT-VZn synthesized by an example of the present invention as a dye sensitizer;

FIG. 6 is a graph of external quantum efficiency (IPCE) of a dye-sensitized solar cell using a polymeric metal complex PBDTT-VZn synthesized in accordance with an embodiment of the present invention as a dye sensitizer.

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.