阅读说明：本技术 四种D-(A’-π-A)2型亚胺衍生物合金属配合物染料敏化剂及其制备方法与用途 (Four kinds of D- (A' -Pi-A)2Imine derivative metal complex dye sensitizer and preparation method and application thereof ) 是由 钟超凡 章厚鹏 徐泽化 吴显明 王凯旋 唐时雨 于 2020-07-29 设计创作，主要内容包括：本发明涉及式1所示的四种D-(A’-π-A)<Sub>2</Sub>型亚胺衍生物合金属配合物BDTT-sf-Cd、BDTT-sf-Zn、BDTT-sf-Cu、BDTT-sf-Ni及其制备方法与用途,它们以功能化的亚胺衍生物作为主配体与金属配位形成的金属配合物为辅助电子配体A’,以苯并二噻吩联二噻吩(BDTT)为电子给体D,通过Heck反应合成D-(A’-π-A)<Sub>2</Sub>结构的亚胺衍生物合金属配合物,实验基于以BDTT-sf-Cd、BDTT-sf-Zn、BDTT-sf-Cu、BDTT-sf-Ni为染料敏化剂的染料敏化太阳能电池的光伏性能测试表现出较好的效果：光电转化效率(PCE)分别达到9.85％、8.99％、8.21％、7.95％,其热分解温度均达到了120℃以上,热稳定性良好,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="397" wi="700" file="DDA0002607394500000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to four kinds of D- (A' -pi-A) shown in formula 1 2 The metal complexes formed by coordination of functional imine derivatives serving as main ligands and metals serve as auxiliary electronic ligands A', benzodithiophene Bithiophene (BDTT) serves as an electronic donor D, and the metal complexes are synthesized through Heck reactionTo D- (A' -Pi-A) 2 The imine derivative alloy metal complex with the structure shows better effects in tests based on the photovoltaic performance of dye-sensitized solar cells taking BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni as dye sensitizers: the Photoelectric Conversion Efficiency (PCE) respectively reaches 9.85%, 8.99%, 8.21% and 7.95%, the thermal decomposition temperature reaches more than 120 ℃, and the thermal stability is good, so that the dye-sensitized solar cell has a certain prospect in the development and application aspects of dye-sensitized solar cells;)

1. Four kinds of D- (A' -Pi-A)₂The type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni have the following structural formulas:

2. the four compounds of claim 1, wherein D- (A' -pi-A)₂The preparation method of the type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni comprises the following steps:

(1) preparation of 5-chloromethyl salicylaldehyde:

weighing paraformaldehyde into a three-necked bottle, slowly adding a large amount of concentrated hydrochloric acid along the wall, after uniformly stirring, slowly dropwise adding salicylaldehyde, wherein the molar ratio of the paraformaldehyde to the salicylaldehyde is 1.8: 1.0-2.2: 1.0, stirring at room temperature for reacting for 36-72 hours, filtering to obtain a crude product white solid, sequentially washing with a saturated sodium bicarbonate solution and distilled water to be neutral, placing in a drying oven for drying, and recrystallizing the crude product with petroleum ether for multiple times to obtain a white needle-shaped solid 5-chloromethyl salicylaldehyde;

(2) preparation of 5-vinyl salicylaldehyde:

adding 5-chloromethyl salicylaldehyde and triphenylphosphine in a molar ratio of 1.8: 1.0-2.2: 1.0 into a three-necked bottle, adding a large amount of benzene, stirring and dissolving, refluxing for 1h at 80 ℃, cooling, filtering, washing the obtained solid for multiple times by using anhydrous ether until filtrate is clear to obtain white powdery solid, drying the above phosphorus salt, carrying out witting reaction, taking the phosphorus salt into the three-necked bottle, adding a large amount of formaldehyde solution, vigorously stirring under the protection of nitrogen in an ice water bath, slowly dropwise adding NaOH solution through a constant-pressure dropping funnel, controlling the system temperature to be below 0 ℃ all the time, stirring and reacting for 8-16 h at normal temperature after the solution is clear, extracting the reaction mixture by using chloroform, drying anhydrous sodium sulfate, filtering and selecting to dry to obtain an orange crude product, passing through a column chromatography, eluting by using a mixture of petroleum ether and ethyl acetate in a volume ratio of 9.0: 1.0-11.0: 1.0, refrigerating and storing, obtaining light yellow crystal 5-vinyl salicylaldehyde;

(3) preparation of 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol:

putting 5-vinyl salicylaldehyde and 3, 4-dimethylaniline with the molar ratio of 1.0: 0.9-1.0: 1.1 into a three-necked bottle, adding absolute ethyl alcohol, stirring until the absolute ethyl alcohol is dissolved, carrying out reflux reaction at 80 ℃ for 8-16 h, cooling, carrying out spin-drying to obtain an orange-yellow solid crude product, recrystallizing the absolute ethyl alcohol for multiple times, and carrying out vacuum drying to obtain a golden yellow solid 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol

(4) Preparation of 5-formyl-8-hydroxyquinoline:

adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-neck flask, dissolving by stirring, slowly adding a sodium hydroxide solution, slowly dropwise adding chloroform under the reflux condition, wherein the molar ratio of 8-hydroxyquinoline to chloroform is 1.0: 2.0-1.0: 2.4, continuously reacting for more than 20 hours, cooling to room temperature, removing the solvent by using a rotary evaporator, pouring into distilled water, acidifying by using 10% of dilute hydrochloric acid until the pH value is about 5, separating out brick red solid, performing suction filtration to obtain an earthy yellow solid crude product, performing vacuum drying, grinding the solid into powder after drying, washing for 8-16 hours by using petroleum ether, and recrystallizing the washed solid by using absolute ethyl alcohol to obtain an orange solid 5-formyl-8-hydroxyquinoline;

(5) preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid:

putting 5-formyl-8-hydroxyquinoline and cyanoacetic acid in a molar ratio of 1.0: 1.4-1.0: 1.6 into a three-necked bottle, adding acetonitrile, stirring to dissolve the acetonitrile, adding a small amount of glacial acetic acid and piperidine, heating to 85 ℃ under the protection of inert gas, reacting for 8-16 h, closing the reaction, performing rotary evaporation until the reaction mixture is nearly saturated, cooling at 0 ℃ for 6-12 h to precipitate crystals, filtering and drying, and recrystallizing the crude product for multiple times by using 25% ethanol to obtain orange solid 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;

(6) preparation of complex sf-Cd:

weighing 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol and 8-hydroxyquinoline derivative in a molar ratio of 1.0: 0.9-1.0: 1.1 into a volumetric three-neck flask, adding tetrahydrofuran, stirring until the tetrahydrofuran is completely dissolved, measuring anhydrous methanol, dissolving Cd (CH) in a beaker₃COO)₂·2H₂O, slowly dropping the solution into the flask by using a constant-pressure dropping funnel, keeping the pH of the system to be weakly acidic, dropping glacial acetic acid or ammonia water for regulation if necessary, heating to 66 ℃, refluxing for 8-16 h, filtering after the system is cooled to room temperature, washing for several times by using deionized water and absolute ethyl alcohol respectively until the filtrate is clear, recrystallizing by using absolute methyl alcohol, and drying in vacuum to obtain a golden yellow solid cadmium metal complex sf-Cd;

(7) preparation of complexes sf-Zn, sf-Cu and sf-Ni:

the complexes sf-Zn, sf-Cu and sf-Ni are synthesized by a synthesis method of reference complexes sf-Cd and by Zn (CH)₃COO)₂·2H₂O、Cu(CH₃COO)₂·2H₂O、Ni(CH₃COO)₂·2H₂O instead of Cd (CH)₃COO)₂·2H₂O, respectively obtaining a light yellow solid zinc metal complex (sf-Zn), an earthy yellow solid copper metal complex (sf-Cu) and a yellow green solid nickel metal complex (sf-Ni) through post-treatment;

(8) preparation of imine derivative metal complex BDTT-sf-Cd:

taking monomer sf-Cd and 2, 6-dibromo-4, 8-di (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b' ] dithiophene monomer with the molar ratio of 1.8: 1.0-2.2: 1.0 into a three-neck flask, adding catalyst palladium acetate and catalyst reducing agent tri (2-tolyl) phosphine, then adding a large amount of refined DMF and a small amount of dried triethylamine, stirring and dissolving under the protection of nitrogen, heating to 90 ℃, carrying out reflux reaction for 36-72 h, lifting to room temperature after the reaction is stopped, filtering to obtain solid in the mixture, washing with anhydrous methanol for a plurality of times, putting into a vacuum drying oven, filtering after adding an appropriate amount of water into the filtrate, washing with anhydrous ethanol, putting the filter cake into the vacuum drying oven completely, taking out after drying, obtaining a yellowish solid imine derivative BDTT-sf-Cd;

(9) preparation of imine derivative metal complexes BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni:

the synthesis of imine derivative metal complexes BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni refers to a BDTT-sf-Cd synthesis method, monomers sf-Zn, sf-Cu and sf-Ni and a donor monomer BDTT are taken to carry out Heck reaction, and gray yellow solid product imine derivative metal complexes BDTT-sf-Zn, wine red solid product imine derivative metal complexes BDTT-sf-Cu and green yellow solid product imine derivative metal complexes BDTT-sf-Ni are obtained after post-treatment.

3. The four compounds of claim 1, wherein D- (A' -pi-A)₂The application of the type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni as dye sensitizers in dye-sensitized solar cells.

Technical Field

The invention relates to four kinds of D- (A' -Pi-A)₂The imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni, the preparation method and the application thereof are research and development and application of photoelectric sensitized materials in Dye Sensitized Solar Cells (DSSCs), and belong to the field of photoelectric materials in new materials.

Background

In the research and development of dye sensitizers, which are the most critical components of dye-sensitized solar cells (DSSCs), it was found that D-a ' -pi-a type organic dye sensitizers using organic moieties such as benzothiadiazole as an auxiliary electron acceptor a ' exhibit superior photovoltaic properties such as absorption properties and photoelectric conversion efficiency compared to D-pi-a type dye sensitizers, and thus the development of D-a ' -pi-a type dye sensitizers began to become the focus and hot spot in this direction. The invention researches and prepares four kinds of D- (A ' -pi-A) by using an imine derivative metal complex which has strong electron-withdrawing capability and can adjust the electron-withdrawing capability by adjusting the coordinate bond strength as an auxiliary electron acceptor A ' and connecting a donor (D) with two acceptor parts (-A ' -pi-A) to increase the electron-withdrawing capability of the acceptor parts₂The dye sensitizers BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni of the type imine derivative metal complex are proved to have good light absorption performance and photovoltaic performance by test application.

Disclosure of Invention

The object of the present invention is to provide and prepare four kinds of D- (A' -pi-A)₂The type imine derivative metal complex is used as a main ligand, benzothiadiaphene bithiophene derivative BDTT is used as an electron donor (D), a complex formed by coordination of a functionalized imine derivative and metal is used as an auxiliary electron acceptor (A'), 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid is coordinated with the metal to form a pi bridge, and the metal complex is used as a metal complex of a functional imine derivative,An acceptor (A) and an anchoring group, four kinds of D- (A '-pi-A) synthesized by linking a donor (D) and a complex acceptor moiety (A' -pi-A) by a Heck reaction₂The metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni have good photoelectric conversion efficiency and thermal stability, and the photovoltaic performance efficiencies of the cells based on BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni as dye sensitizers respectively reach 9.85%, 8.99%, 8.21% and 7.95%, and the structural general formulas are as follows:

four kinds of D- (A' -Pi-A)₂The preparation method of the type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni comprises the following steps:

(1) preparation of 5-chloromethyl salicylaldehyde:

weighing paraformaldehyde into a three-necked bottle, slowly adding a large amount of concentrated hydrochloric acid along the wall, after uniformly stirring, slowly dropwise adding salicylaldehyde, wherein the molar ratio of the paraformaldehyde to the salicylaldehyde is 1.8: 1.0-2.2: 1.0, stirring at room temperature for reacting for 36-72 hours, filtering to obtain a crude product white solid, sequentially washing with a saturated sodium bicarbonate solution and distilled water to be neutral, placing in a drying oven for drying, and recrystallizing the crude product with petroleum ether for multiple times to obtain a white needle-shaped solid 5-chloromethyl salicylaldehyde;

(2) preparation of 5-vinyl salicylaldehyde:

adding 5-chloromethyl salicylaldehyde and triphenylphosphine in a molar ratio of 1.8: 1.0-2.2: 1.0 into a three-necked bottle, adding a large amount of benzene, stirring and dissolving, refluxing for 1h at 80 ℃, cooling, filtering, washing the obtained solid for multiple times by using anhydrous ether until filtrate is clear to obtain white powdery solid, drying the above phosphorus salt, carrying out witting reaction, taking the phosphorus salt into the three-necked bottle, adding a large amount of formaldehyde solution, vigorously stirring under the protection of nitrogen in an ice water bath, slowly dropwise adding NaOH solution through a constant-pressure dropping funnel, controlling the system temperature to be below 0 ℃ all the time, stirring and reacting for 8-16 h at normal temperature after the solution is clear, extracting the reaction mixture by using chloroform, drying anhydrous sodium sulfate, filtering and selecting to dry to obtain an orange crude product, passing through a column chromatography, eluting by using a mixture of petroleum ether and ethyl acetate in a volume ratio of 9.0: 1.0-11.0: 1.0, refrigerating and storing, obtaining light yellow crystal 5-vinyl salicylaldehyde;

(3) preparation of 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol:

putting 5-vinyl salicylaldehyde and 3, 4-dimethylaniline with the molar ratio of 1.0: 0.9-1.0: 1.1 into a three-necked bottle, adding absolute ethyl alcohol, stirring until the absolute ethyl alcohol is dissolved, carrying out reflux reaction at 80 ℃ for 8-16 h, cooling, and then carrying out spin drying to obtain an orange-yellow solid crude product, recrystallizing the absolute ethyl alcohol for multiple times, and carrying out vacuum drying to obtain a golden yellow solid 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol;

(4) preparation of 5-formyl-8-hydroxyquinoline:

adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-neck flask, dissolving by stirring, slowly adding a sodium hydroxide solution, slowly dropwise adding chloroform under the reflux condition, wherein the molar ratio of 8-hydroxyquinoline to chloroform is 1.0: 2.0-1.0: 2.4, continuously reacting for more than 20 hours, cooling to room temperature, removing the solvent by using a rotary evaporator, pouring into distilled water, acidifying by using 10% of dilute hydrochloric acid until the pH value is about 5, separating out brick red solid, performing suction filtration to obtain an earthy yellow solid crude product, performing vacuum drying, grinding the solid into powder after drying, washing for 8-16 hours by using petroleum ether, and recrystallizing the washed solid by using absolute ethyl alcohol to obtain an orange solid 5-formyl-8-hydroxyquinoline;

(5) preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid:

putting 5-formyl-8-hydroxyquinoline and cyanoacetic acid in a molar ratio of 1.0: 1.4-1.0: 1.6 into a three-necked bottle, adding acetonitrile, stirring to dissolve the acetonitrile, adding a small amount of glacial acetic acid and piperidine, heating to 85 ℃ under the protection of inert gas, reacting for 8-16 h, closing the reaction, performing rotary evaporation until the reaction mixture is nearly saturated, cooling at 0 ℃ for 6-12 h to precipitate crystals, filtering and drying, and recrystallizing the crude product for multiple times by using 25% ethanol to obtain orange solid 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;

(6) preparation of complex sf-Cd:

taking 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol and 8-hydroxyquinoline derivative in a molar ratio of 1.0: 0.9-1.0: 1.1 into a volumetric three-neck flask, adding tetrahydrofuran, stirring until the tetrahydrofuran is completely dissolved, measuring anhydrous methanol, dissolving Cd (CH) in a beaker₃COO)₂·2H₂O, slowly dropping the solution into the flask by using a constant-pressure dropping funnel, keeping the pH of the system to be weakly acidic, dropping glacial acetic acid or ammonia water for regulation if necessary, heating to 66 ℃, refluxing for 8-16 h, filtering after the system is cooled to room temperature, washing for several times by using deionized water and absolute ethyl alcohol respectively until the filtrate is clear, recrystallizing by using absolute methyl alcohol, and drying in vacuum to obtain a golden yellow solid cadmium metal complex sf-Cd;

(7) preparing metal complexes sf-Zn, sf-Cu and sf-Ni:

the complexes sf-Zn, sf-Cu and sf-Ni are synthesized by a synthesis method of reference complexes sf-Cd and by Zn (CH)₃COO)₂·2H₂O、Cu(CH₃COO)₂·2H₂O、Ni(CH₃COO)₂·2H₂O instead of Cd (CH)₃COO)₂·2H₂O, respectively obtaining a light yellow solid zinc metal complex (sf-Zn), an earthy yellow solid copper metal complex (sf-Cu) and a yellow green solid nickel metal complex (sf-Ni) through post-treatment;

(8) preparation of imine derivative metal complex BDTT-sf-Cd:

taking monomer sf-Cd and 2, 6-dibromo-4, 8-di (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b' ] dithiophene monomer with the molar ratio of 1.8: 1.0-2.2: 1.0 into a three-neck flask, adding catalyst palladium acetate and catalyst reducing agent tri (2-tolyl) phosphine, then adding a large amount of refined DMF and a small amount of dried triethylamine, stirring and dissolving under the protection of nitrogen, heating to 90 ℃, carrying out reflux reaction for 36-72 h, lifting to room temperature after the reaction is stopped, filtering to obtain solid in the mixture, washing with anhydrous methanol for a plurality of times, putting into a vacuum drying oven, filtering after adding an appropriate amount of water into the filtrate, washing with anhydrous ethanol, putting the filter cake into the vacuum drying oven completely, taking out after drying, obtaining a yellowish solid imine derivative BDTT-sf-Cd;

(9) preparation of imine derivative metal complexes BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni:

according to the method for synthesizing the imine derivative metal complexes BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni according to the BDTT-sf-Cd reference, monomers sf-Zn, sf-Cu and sf-Ni and a donor monomer BDTT are taken to carry out Heck reaction, and gray yellow solid product imine derivatives BDTT-sf-Zn, wine red solid product imine derivatives BDTT-sf-Cu and green yellow solid product imine derivatives BDTT-sf-Ni are obtained after post-treatment.

Four kinds of D (-A' -Pi-A)₂The application of the type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni: a dye sensitizer material for use in a dye-sensitized solar cell for absorbing sunlight and generating and transporting electrons;

the main advantages of the invention are: (1) four kinds of D- (A' -Pi-A)₂An imine derivative metal complex, which is synthesized by taking benzothiadiazole bithiophene derivative BDTT as an electron donor (D), taking a complex formed by coordination of a functionalized imine derivative and metal as an auxiliary electron acceptor (A '), coordinating 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid and metal to form a pi bridge, an acceptor (A) and an anchoring group, and connecting the donor (D) and a complex acceptor part (-A' -pi-A) through a Heck reaction₂The type imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni show excellent photovoltaic performance and photoelectric conversion efficiency, the preparation method is simple, and the raw materials are easy to obtain; (2) the material has good thermal property and light stability, and is beneficial to practical application;

drawings

FIG. 1 NMR spectra of ligand 5-chloromethyl salicylaldehyde synthesized in the example of the present invention: (¹HNMR)(400MHz，CDCl₃，ppm)；

FIG. 2 NMR spectra of ligand 5-vinyl salicylaldehyde synthesized in the example of the invention: (¹HNMR)(400MHz，CDCl₃，ppm)；

FIG. 3 ligand 2- (((3, 4-dimethylphenyl) phenylene) synthesized by an example of the inventionNuclear magnetic resonance hydrogen spectrum of amino) methyl) -4-vinylphenol¹HNMR)(400MHz，CDCl₃，ppm)；

FIG. 4 NMR spectra of ligand 5-formyl-8-hydroxyquinoline synthesized according to example of the invention: (¹HNMR)(400MHz，CDCl₃，ppm)；

FIG. 5 NMR spectra of ligand 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid synthesized in accordance with example of the invention: (¹HNMR)(400MHz，CDCl₃，ppm)；

FIG. 6 Infrared Spectroscopy (FTIR) (KBr, cm) of complexes sf-Cd, sf-Zn, sf-Cu, sf-Ni synthesized by the example of the invention^-1)；

FIG. 7 Infrared Spectroscopy (FTIR) (KBr, cm) of the compounds BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu, BDTT-sf-Ni synthesized according to the example of the invention^-1)；

FIG. 8 is a thermogravimetric analysis (TGA) of the compounds BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu, BDTT-sf-Ni synthesized by the examples of the present invention;

FIG. 9 is a current density-voltage (J-V) curve of a dye-sensitized solar cell using BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni compounds synthesized according to an example of the present invention as dye sensitizers;

FIG. 10 is a graph showing external quantum efficiency (IPCE) curves of dye-sensitized solar cells using BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu, BDTT-sf-Ni compounds synthesized according to examples of the present invention as dye sensitizers;

Detailed Description

The reaction synthesis route of the imine derivative metal complex BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni is shown as formula 2;

four kinds of D- (A' -Pi-A)₂The molecular structural formula of the metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni of the type imine derivatives is as follows:

the preparation method of the imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni comprises the following steps:

preparation of 5-chloromethyl salicylaldehyde: weighing paraformaldehyde (9.10g, 0.303mol) into a 250mL three-necked bottle, slowly adding 90mL concentrated hydrochloric acid along the wall, and slowly stirring uniformly

Synthesis route of imine derivative metal complexes BDTT-sf-Cd, BDTT-sf-Zn, BDTT-sf-Cu and BDTT-sf-Ni of formula 2

Slowly dropwise adding salicylaldehyde (15.6mL, 0.15mol), stirring at room temperature for reaction for 48 hours, filtering to obtain a crude product white solid, sequentially washing with a saturated sodium bicarbonate solution and distilled water to be neutral, placing in a drying oven for drying, recrystallizing the crude product with petroleum ether for three times to obtain 16.8g of white needle-like solid, wherein the yield is 66 percent, m.p.85-86 ℃, and nuclear magnetic resonance hydrogen spectrum¹H-NMR) is shown in figure 1,¹H-NMR(CDCl₃,ppm):11.09(s,1H),9.90(s,1H),7.62(s,1H),7.55(d, 1H),7.03(d,1H),4.64(s,2H).¹³C-NMR(CDCl₃,ppm):196.22,161.63, 135.86,133.66,129.24,120.37,117.74,46.20；

b.5-preparation of vinyl salicylaldehyde: adding 5-chloromethyl salicylaldehyde (3.48g, 20.5mmol) and triphenylphosphine (5.25g, 40mmol) into a 250mL three-neck flask, adding 70mL of benzene, stirring and dissolving, refluxing for 1h at 80 ℃, cooling, filtering, washing the obtained solid with anhydrous ether for three times until the filtrate is clear to obtain 6.88g of white powdery solid, the yield is 87%, m.p.253-254 ℃, drying the above phosphonium salt, carrying out witting reaction, taking 3.89g of phosphonium salt into a 100mL three-neck flask, adding 30mL of formaldehyde solution, stirring vigorously under the protection of nitrogen in an ice water bath, slowly dropwise adding 14 mol. L through a constant-pressure dropping funnel^-1NaOH solution (5g NaOH,8.9 mL H)₂O), controlling the temperature of the system to be below 0 ℃ all the time, stirring the solution at normal temperature for reaction for 12h after the solution becomes clear, extracting the reaction mixture by using chloroform, drying the solution by using anhydrous sodium sulfate, filtering and selecting the solution to be dry to obtain an orange crude product, passing the orange crude product through a column chromatography, using petroleum ether/ethyl acetate as an eluent to be 10:1(v/v), and refrigerating the orange crude product at low temperature to obtain light yellow crystals, wherein the yield is 49 percent, and the m.p. is 19-20 DEG CNuclear magnetic resonance hydrogen spectrum (¹H-NMR) is shown in figure 2,¹H-NMR(CDCl₃,ppm): 11.03(s,1H),9.92(s,1H),7.64(d,1H),7.56(s,1H),6.99(d,1H), 6.65-6.72(m,1H),5.62-5.72(d,1H),5.25-5.28(d,1H).¹³C-NMR(CDCl₃, ppm):191.05,161.05,136.48,136.12,130.84,129.14,127.71,118.41, 114.28；

preparation of C.2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol: weighing 5-vinyl salicylaldehyde (1.48g, 10mmol) and 3, 4-dimethylaniline (1.21g, 10mmol) in a 50mL three-necked bottle, adding 20mL of absolute ethyl alcohol, stirring until the absolute ethyl alcohol is dissolved, carrying out reflux reaction at 80 ℃ for 12h, cooling and then carrying out spin drying to obtain an orange yellow solid crude product, recrystallizing the absolute ethyl alcohol for three times, carrying out vacuum drying to obtain a golden yellow solid product 2.14g, wherein the yield is 85%, m.p.58-59 ℃, and carrying out nuclear magnetic resonance hydrogen spectrum (NMR)¹H-NMR) is shown in figure 3,¹H-NMR(CDCl₃,ppm):13.54(s,1H), 8.63(s,1H),7.40-7.47(m,Ar-H),7.10-7.26(m,Ar-H),7.00-7.06(d,1H), 6.63-6.78(m,1H),5.62-5.66(d,1H),5.15-5.18(d,1H),2.29-2.31(ds, 6H).¹³C-NMR(CDCl₃,ppm):161.33,161.01,146.01,144.40,137.78,135.75,130.53,130.48,129.97,128.90,122.48,119.07,118.28,117.46, 111.79,19.92,19.43；

preparation of 5-formyl-8-hydroxyquinoline: 25g (172mmol) of 8-hydroxyquinoline and 100ml of absolute ethanol were put into a 250ml three-necked flask, dissolved by stirring, and then a sodium hydroxide solution (50 g of sodium hydroxide was dissolved in 50ml of distilled water) was slowly added thereto, and 45g (383mmol) of chloroform was slowly added dropwise under reflux, followed by further reaction for 20 hours. Cooling to room temperature, removing the solvent by a rotary evaporator, pouring into 600ml of distilled water, acidifying with dilute hydrochloric acid prepared by using concentrated hydrochloric acid and distilled water in a volume ratio of 1: 4 until the pH is about 5, separating out brick red solid, performing suction filtration to obtain a crude product of an earth yellow solid, performing vacuum drying, grinding the solid into powder after drying, extracting with petroleum ether for 12 hours, and recrystallizing the extracted solid with absolute ethyl alcohol to obtain 4.3g of an orange solid with the yield of 14.4%; m.p.172.2-173.5 ℃; nuclear magnetic resonance hydrogen spectrum (¹H-NMR) is shown in figure 4,¹H-NMR(CDCl₃,ppm):10.14(s,1H),9.68-9.69 (d,1H),8.89-8.96(d,1H),7.98-8.02(d,1H),7.65-7.68(q,1H),7.29-7.31 (d,1H).¹³C-NMR(CDCl₃,ppm):192.07，157.84，148.74，140.48，137.85，134.77，126.59，124.74，123.56，108.99；

preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid: putting weighed 5-formyl-8-hydroxyquinoline (0.5190g, 3.0mmol) and cyanoacetic acid (0.3830g, 4.5mmol) into a 50mL three-necked bottle, adding 20mL acetonitrile, stirring to dissolve the acetonitrile, adding 3mL glacial acetic acid and 4 drops of piperidine, heating to 85 ℃ under the protection of inert gas for reaction for 12h, closing the reaction, performing rotary evaporation until the reaction mixture is nearly saturated, cooling at 0 ℃ for 8h to precipitate crystals, filtering and drying, recrystallizing the crude product with 25% ethanol for three times to obtain 0.4250g of orange solid, wherein the yield is 59%, m.p.200-201 ℃, and FT-IR (KBr, cm, etc.)^-1) 3447(O-H),2220(C ≡ N),1580(C ≡ C),1530(C ═ N)¹HNMR) see figure 5 of the accompanying drawings,¹H-NMR(CDCl₃,ppm):8.96(d,1H,Ar-H),8.87(d,2H,-CH＝),8.62(d, 1H,Ar-H),8.42(d,1H,Ar-H),7.71(q,1H,Ar-H),7.26(d,1H,Ar- H)，¹³C-NMR(DMSO-d₆,ppm):164.19,159.14,150.06,149.46,138.71, 132.60,131.17,128.73,123.95,118.88,117.24,112.18,102.99.Anal.Calcd.for[C₁₃H₈N₂O₃]:C,65.00；H,3.36；N,11.66％.Found:C,65.22；H, 2.94；N,11.61％；

F. preparing a cadmium metal complex sf-Cd: weighing main ligand 2- (((3, 4-dimethylphenyl) imino) methyl) -4-vinylphenol (0.251g, 1mmol) and auxiliary ligand 8-hydroxyquinoline derivative (0.242g, 1mmol) in a 150mL three-neck flask, measuring 30mL tetrahydrofuran, adding, stirring until the tetrahydrofuran is completely dissolved, measuring 15mL absolute methanol, dissolving 0.293g (1.1mmol) Cd (CH) in a beaker₃COO)₂·2H₂O, slowly dripping into the flask by using a constant-pressure dropping funnel, keeping the pH of the system to be weakly acidic, dripping glacial acetic acid or ammonia water for regulation if necessary, heating to 66 ℃, refluxing for 12h, filtering after the system is cooled to room temperature, washing for several times by using deionized water and absolute ethyl alcohol respectively until the filtrate is clear, recrystallizing by using absolute methyl alcohol, and drying in vacuum to obtain a golden yellow solid of 0.356g, wherein the yield is 59%, and an infrared spectrogram (FT-IR) is shown in figure 6, and FT-IR (KBr, cm) is shown in the specification^-1):3421(O-H),2213(C≡N),1600(C＝C), 1560(C＝N),1101(C-O-Cd),496(N-Cd).Anal.Calcd.for [C₂₆H₂₄N₂O₂Cd]:C,61.36；H,4.75；N,5.50.Found:C,61.73；H,4.22；N,5.54％；

G. Preparation of zinc metal complex sf-Zn:

the zinc metal complex sf-Zn is synthesized by a synthesis method referring to cadmium metal complex sf-Cd, and Zn (CH)₃COO)₂·2H₂O (0.241g, 1.1mmol) instead of Cd (CH)₃COO)₂·2H₂O, 0.328g of a pale yellow solid is obtained, yield 63%; infrared spectrum (FT-IR) (KBr, cm)^-1) See FIG. 6, FT-IR (KBr, cm)^-1):3421(O-H),2213(C≡N),1620(C＝C),1566(C＝N), 1101(C-O-Zn),507(N-Zn).Anal.Calc-d.for[C₂₈H₂₇N₂O₄Zn]:C,64.56；H,5.22；N,5.38.Found:C,64.29；H,5.36；N,5.92％；

H. Preparing a copper metal complex sf-Cu:

the copper metal complex sf-Cu is synthesized by a synthesis method referring to cadmium metal complex sf-Cd, and Cu (CH)₃COO)₂·H₂O (0.219g, 1.1mmol) instead of Cd (CH)₃COO)₂·2H₂O, 0.291g of a yellowish brown solid is obtained in a yield of 56%; infrared spectrum (FT-IR) (KBr, cm)^-1) See FIG. 6, FT-IR (KBr, cm)^-1):3413(O-H),2212(C≡N),1606(C＝C),1570(C＝N),1109(C-O-Cu),522( N-Cu).Anal.Calcd.for[C₂₈H₂₇N₂O₄Cu]:C,64.79；H,5.24；N,5.40. Found:C,64.91；H,5.54；N,5.57％；

I. Preparation of nickel complex sf-Ni:

the nickel complex sf-Ni is synthesized by a synthesis method referring to cadmium metal complex sf-Cd and by using Ni (CH)₃COO)₂·4H₂O (0.273g, 1.1mmol) instead of Cd (CH)₃COO)₂·2H₂O, to give 0.245g of a yellowish green solid in a yield of 54%, infra-red spectrum (FT-IR) (KBr, cm)^-1) See FIG. 6, FT-IR (KBr, cm)^-1):3440(O-H),2213(C≡N),1610(C＝C),1570(C＝N),1110(C-O-Ni),496(N-Ni).Anal.Calcd.for[C₂₆H₂₄N₂O₂Ni]: C,68.61；H,5.31；N,6.15.Found:C,68.74；H,5.61；N,6.71％；

J. Preparation of imine derivative metal complex BDTT-sf-Cd:

metal complex BDTT-sf-Cd is synthesized according to Heck polymerization reaction, and complex monomers sf-Cd (0.1885g,0.308mmol),2, 6-dibromo-4, 8-di (5- (2-ethyloctyl) thiophen-2-yl) benzo [1,2-b:4,5-b']Dithiophene donor monomer (0.111g,0.151mmol) was placed in a three-necked flask, and palladium acetate (Pd (CH) as a catalyst was added₃COO)₂0.0029g and 0.013mmol) and a catalyst reducing agent tris (2-tolyl) phosphine (0.0304g and 0.102mmol), then adding refined DMF15mL and 3mL of dried triethylamine, stirring and dissolving under the protection of nitrogen, then heating to 90 ℃, refluxing for 48 hours, lifting and cooling to room temperature after the reaction is stopped, filtering to obtain a solid in the mixture, washing with anhydrous methanol for a plurality of times, then placing in a vacuum drying oven, adding an appropriate amount of water into the filtrate, filtering, washing with anhydrous ethanol, then placing the filter cake in the vacuum drying oven, completely drying, and then taking out to obtain 0.148g of a light yellow solid, wherein the yield is 55%, and an infrared spectrum (FT-IR) is shown in figure 7, and FT-IR (KBr, cm) is shown in figure 7^-1):3428(O-H),2926,2850(C-H), 2206(C≡N),1620(C＝C),1560(C＝N),1101(C-O-Cd),533(N-Cd). Anal.Calcd.for[C₉₄H₈₄N₆O₈S₄Cd₂]:C,63.47；H,4.76；N,4.72；S,7.21. Found:C,62.66；H,4.83；N,4.64；S,7.16％.Mn＝1.78Kg/mol；

K. Preparation of imine derivative metal complex BDTT-sf-Zn:

synthesis of imine derivative metal complex BDTT-sf-Zn referring to a BDTT-sf-Cd method, zinc metal complex monomer sf-Zn (0.4447g,0.787mmol) and donor monomer BDTT (0.2902g,0.394mmol) are weighed to carry out Heck reaction, and after post-treatment, a gray yellow solid product 0.292g is obtained, the yield is 44%, an infrared spectrogram (FT-IR) is shown in figure 7, and FT-IR (KBr, cm) is shown in figure 7^-1):3420(O-H),2213(C≡N),1660(C＝O),1606(C＝C), 1560(C＝N),1106(C-O-Zn),508(N-Zn).Anal.Calcd.for [C₉₄H₈₄N₆O₈S₄Zn₂]:C,67.02；H,5.03；N,4.99；S,7.61.Found:C,67.15； H,5.03；N,4.61；S,7.08％.Mn＝1.68Kg/mol；

Preparation of imine derivative complex BDTT-sf-Cu:

obtaining of an imine derivative metal complex BDTT-sf-Cu refers to a synthesis method of BDTT-sf-Cd, copper metal complex monomer sf-Cu (0.2898g,0.514mmol) and donor monomer BDTT (0.190g,0.257mmol) are weighed to carry out Heck polymerization, and a wine red solid product is obtained after filtration and drying, wherein the yield is 59%; the infrared spectrum (FT-IR) is shown in figure 7, and FT-IR (KBr, cm)^-1):3425(O-H),2920,2850(C-H),2210(C≡N), 1600(C＝C),1575(C＝N),1109(C-O-Cu),517(N-Cu).Anal.Calcd.for [C₉₄H₈₄N₆O₈S₄Cu₂]:C,67.16；H,5.04；N,5.00；S,7.63.Found:C,67.37； H,4.75；N,5.22；S,7.82％.Mn＝1.68Kg/mol；

M, preparation of imine derivative metal complex BDTT-sf-Ni:

obtaining of imine derivative metal complex BDTT-sf-Ni referring to a synthesis method of BDTT-sf-Cd, weighing nickel metal complex monomer sf-Ni (0.164g,0.300mmol) and donor monomer BDTT (0.110g,0.160mmol) to carry out Heck polymerization reaction, washing with deionized water and absolute ethyl alcohol for three times after filtering, drying to obtain a green yellow solid product 0.166g with a yield of 66%, and an infrared spectrogram (FT-IR) shown in figure 7, wherein FT-IR (KBr, cm) is shown in the specification^-1): 3410(O-H),2210(C≡N),1660(C＝O),1620(C＝C),1566(C＝N), 1110(C-O-Ni),507(N-Ni).Anal.Calcd.for[C₉₄H₈₄N₆O₈S₄Ni₂]:C, 67.55；H,5.07；N,5.03；S,7.67.Found:C,68.44；H,5.21；N,5.92；S,7.29％.Mn＝1.67Kg/mol。