CN114957623A - Three copolymerization complexes taking benzodithiophene derivatives as ligands, and preparation method and application thereof - Google Patents

Three copolymerization complexes taking benzodithiophene derivatives as ligands, and preparation method and application thereof Download PDF

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CN114957623A
CN114957623A CN202210636927.9A CN202210636927A CN114957623A CN 114957623 A CN114957623 A CN 114957623A CN 202210636927 A CN202210636927 A CN 202210636927A CN 114957623 A CN114957623 A CN 114957623A
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钟超凡
马银峰
章厚鹏
田勇
刘惠敏
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Abstract

The invention relates to three novel copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni shown as a formula 1 and using benzodithiophene derivatives BDTT as an electron donor D and 2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b']The complex formed by coordination of bithiophene and metal is an auxiliary electron acceptor A ', 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid is used as an electron acceptor, a pi bridge and an anchoring group, and a D-A' -pi-A type polymeric complex is synthesized through Yamamoto coupling reaction, and the experimental test shows better effects in the photovoltaic performance test of the dye-sensitized solar cell based on the dye sensitizer of the polymeric complex: the photoelectric conversion efficiency is 10.01 percent,8.25 percent and 6.91 percent, the thermal decomposition temperature of the dye sensitized solar cell reaches above 243 ℃, and the thermal stability is good, so the dye sensitized solar cell has a certain prospect in the development and application aspect of the dye sensitized solar cell;

Description

Three copolymerization complexes taking benzodithiophene derivatives as ligands, and preparation method and application thereof
Technical Field
The invention relates to three novel copolymerization complexes taking benzodithiophene derivatives as ligands, a preparation method thereof and application of the copolymerization complexes serving as dye sensitizers in dye-sensitized solar cells, belonging to the field of photoelectric materials in novel materials.
Background
Dye Sensitized Solar Cells (DSSCs) have received a great deal of attention from researchers since their advent, in which TiO is adsorbed 2 The dye sensitizer has an important influence on the power conversion efficiency of the DSSCs; the most common structure in the dye is a donor-pi bridge-acceptor (D-pi-A) structure, but the structure has some inevitable defects, such as poor dye stability, narrow absorption range, difficult adjustment of electron push-pull balance between the donor (D) and the acceptor (A), and the like, recently, researchers have introduced a D-A '-pi-A structure of an auxiliary electron acceptor A' on the basis of the D-pi-A structure, so that the push-pull and electron transmission capabilities are enhanced, the recombination of electrons is reduced, the photoelectric conversion efficiency is obviously improved, the auxiliary electron acceptor A 'is generally an organic electron-withdrawing body which has weak electron-withdrawing capability and is inconvenient to adjust, such as benzothiazole and the like, the metal complex is used for replacing organic compounds such as benzothiadiazole and the like as the auxiliary electron acceptor A', and the strength and the type of a coordinate bond are changed, the energy level of the track is adjusted, the charge separation is accelerated, and the electron-withdrawing capability of the auxiliary electron acceptor is improved, so that the photovoltaic performance is improved; three D-A' -Pi-A type copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands are designed and synthesized, and test application shows that the three polymerization complex dye sensitizers have good light absorption performance and photovoltaic performance.
Disclosure of Invention
The invention aims to provide and prepare three novel D-A' -Pi-A type polymeric complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni for being used as photoelectric dye sensitizers in dye-sensitized solar cells; the dye sensitizer is prepared by taking benzodithiophene derivative BDTT as an electron donor D, taking benzodithiophene derivative and metal to coordinate to form a main ligand A ', taking 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid as an electron acceptor, a pi bridge and an anchoring group, and polymerizing the electron donor D and an electron acceptor part (-A' -pi-A) through Yamamoto coupling reaction to form three polymerization complex dye sensitizers, wherein the complex has good photoelectric conversion efficiency and thermal stability, the photovoltaic performance efficiency of a battery based on the three polymerization complex dye sensitizers respectively reaches 10.01%, 8.25% and 6.91%, and the structural general formula is as follows:
Figure BDA0003680727880000021
three new preparation methods of copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands are disclosed:
(1) preparation of 1, 2-bithiophene-1, 2-dione:
adding thiophene-3-formaldehyde and potassium carbonate into a single-neck flask according to the molar ratio of 1.0: 1.0-1.0: 3.0, then adding a solvent DMSO and 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide into the flask, heating to 60 ℃ in the atmosphere of carbon dioxide to react for 32-40 h, cooling to room temperature after the reaction is finished, extracting with anhydrous ether for three times, collecting an organic phase, adding anhydrous magnesium sulfate, drying for 10-14 h, filtering, and spin-drying to obtain a crude product, drying the crude product completely, and performing column separation by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 10-1: 14 as an eluent to obtain a golden yellow acicular solid 1, 2-dithiophene-1, 2-dione;
(2) benzo [1,2-b: preparation of 6,5-b' ] dithiophene-4, 5-dione:
adding dichloromethane and 1, 2-dithiophene-1, 2-diketone into a single-neck flask in sequence, and then slowly adding FeCl 3 Stirring for 20-26 h, and mixing the 1, 2-dithiophene-1, 2-dione and FeCl 3 In a molar ratio of 1: 4-1: and 6, standing after the reaction is finished, adding a proper amount of water, extracting with a proper amount of dichloromethane, collecting an organic phase, drying for 20-28 hours by using anhydrous magnesium sulfate, filtering, and then carrying out spin-drying to obtain a crude product, and carrying out column separation on the crude product by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 10-1: 14 as an eluent to obtain black needle-shaped solid benzo [1,2-b: 6,5-b']Dithiophene-4, 5-dione;
(3)2, 7-dibromobenzo [1,2-b: preparation of 6,5-b' ] dithiophene-4, 5-dione:
in a single-neck flask, benzo [1,2-b: 6,5-b' ] dithiophene-4, 5-dione, NBS and DMF, benzo [1,2-b: the molar ratio of 6,5-b' ] dithiophene-4, 5-dione to NBS is 1: 1-1: and 3, heating to 70 ℃ for reaction for 20-28 h, cooling to room temperature after the reaction is finished, standing to enable the solid to be completely separated out, and drying after suction filtration to obtain a light blue solid 2, 7-dibromobenzo [1,2-b: 6,5-b' ] dithiophene-4, 5-dione;
(4) preparation of 2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b' ] -dithiophene:
mixing the components in a molar ratio of 1.0: 1.0: 0.5: 6.2-1.0: 1.2: 0.7: 6.4 2, 7-dibromobenzo [1,2-b: adding 6,5-b '] dithiophene-4, 5-dione, n-bromoethane, tetrabutyl ammonium bromide and sodium hydrosulfite into a three-neck flask, adding tetrahydrofuran aqueous solution, slowly dropwise adding KOH aqueous solution through a constant-pressure dropping funnel under the protection of nitrogen, slowly heating to 80 ℃ after dropwise adding, reacting for 44-52 h, cooling to room temperature after reaction, extracting with ethyl acetate, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, and spin-drying to obtain a light yellow crude liquid product, and performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether as an eluent in a volume ratio of 1: 30-1: 50 to obtain a yellow liquid product 2, 7-dibromo-4, 5-dibutoxy- [2,1-b:3,4-b' ] -dithiophene;
(5) preparation of 5-formyl-8-hydroxyquinoline:
adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-necked flask, adding a sodium hydroxide solution through a constant-pressure separating funnel under the stirring state, heating to 80 ℃ for reflux after complete dissolution, slowly adding chloroform through the constant-pressure separating funnel, wherein the molar ratio of the 8-hydroxyquinoline to the chloroform is 1.0: 2.0-1.0: 3.0, continuously reacting for 20-28 h, cooling to room temperature, removing the solvent by using a rotary evaporator, pouring the product into distilled water, adjusting the pH to be about 7, generating a large amount of brown solid at the moment, performing suction filtration to obtain the brown solid, obtaining a brown blocky object after complete vacuum drying, grinding to obtain a powdery solid, continuously drying, washing by using petroleum ether after complete drying, naturally cooling the washing liquid overnight to separate out an orange solid, filtering supernatant, recrystallizing the remaining solid twice by using the absolute ethyl alcohol, and completely drying the obtained solid, obtaining orange pink filiform crystal 5-formyl-8-hydroxyquinoline;
(6) 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 and a small amount of acetic acid, stirring to dissolve the acetonitrile and the small amount of acetic acid, adding a small amount of piperidine, heating a system to 90 ℃, reacting for 32-40 h, closing the reaction, spin-drying the solvent, putting the system into a vacuum drying oven until the solvent is completely dried to obtain a yellow blocky crude product, grinding the crude product into powder, washing the solid with trichloromethane for three times, drying the solid, and recrystallizing the solid with ethanol for two times to obtain orange solid powder 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;
(7) preparation of metal complex BET-Zn:
taking the molar ratio of 1.0: 1.0-1.0: 2.0 of 2, 7-dibromo-4, 5-dibutoxy- [2,1-b:3,4-b']Adding bithiophene and 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid into a single-mouth bottle in sequence, heating to 40 ℃ to dissolve, and then adding Zn (CH) 3 COO) 2 ·2H 2 Dissolving O in anhydrous methanol, slowly dropwise adding the dissolved O through a constant-pressure funnel, heating to 75 ℃, reacting for 20-28 h, cooling to room temperature after the reaction is finished, putting the reaction product into a refrigerator overnight to completely separate out solids, filtering, washing with water for three times, and washing with anhydrous ethanol for three times to finally obtain a yellow solid zinc-containing complex BET-Zn;
(8) preparation of metal complexes BET-Cu and BET-Ni:
the synthesis method of the complex (BET-Cu, BET-Ni) is the same as that of the complex (BET-Zn), and Zn (CH) 3 COO) 2 ·2H 2 Changing O to Cu (CH) respectively 3 COO) 2 ·2H 2 O、Ni(CH 3 COO) 2 ·4H 2 O, respectively synthesizing to obtain a brown solid copper-containing complex BET-Cu and an orange-red solid nickel-containing complex BET-Ni;
(9) preparation of polymeric Metal Complex BDTT-BET-Zn:
taking the molar ratio of 1.0: 0.9 to 1.0: adding a complex monomer (BET-Zn) and 2, 6-dibromo-4, 8-di (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b '] dithiophene (BDTT) into a single-neck flask, then adding zinc powder, triphenylphosphine, bis (triphenylphosphine) nickel dichloride and 2, 2' -bipyridine, then adding DMF, carrying out reflux reaction for 44-52 h under the protection of nitrogen, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying to obtain a brown solid powdery product BDTT-BET-Zn;
(10) synthesizing a polymeric metal complex BDTT-BET-Cu and BDTT-BET-Ni;
according to the synthesis method of the polymers (BDTT-BET-Cu and BDTT-BET-Ni), referring to the synthesis of BDTT-BET-Zn, zinc metal complexes (BET-Zn) required by the reaction are respectively changed into metal complexes (BET-Cu and BET-Ni), and the dark brown solid powder polymerization complexes BDTT-BET-Cu and the dark brown solid powder polymerization complexes BDTT-BET-Ni are respectively synthesized;
use of three novel polymeric complexes: a dye sensitizer used in a dye-sensitized solar cell for absorbing sunlight and generating and transmitting electrons;
the main advantages of the invention are: (1) the invention discloses a polymerization complex with three novel thiophene derivatives as ligands, wherein a benzodithiophene bithiophene derivative BDTT is used as a donor (D), 2, 7-dibromo-4, 5-dibutoxy- [2,1-b:3,4-b '] -bithiophene is used as a main ligand, the main ligand is respectively coordinated with three metals to form an auxiliary receptor A', 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid is used as an electron receptor, a pi bridge and an anchoring group, and the donor and the complex are connected through Yamamoto coupling reaction, so that the complex has good photoelectric conversion efficiency and thermal stability; (2) the electrochemical performance, the thermal performance and the light stability are good, and the practical application is facilitated;
drawings
FIG. 1 Synthesis of ligand 1, 2-dithiophene-1, 2-dione 1 H-NMR Nuclear magnetic resonance Hydrogen Spectrum of spectrogram ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 2 ligand benzo [1,2-b: 6,5-b']NMR spectrum of dithiophene-4, 5-dione (II) 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 3 shows the reaction conditions of ligand 2, 7-dibromobenzo [1,2-b: 6,5-b']Nuclear magnetic resonance of the synthesis of dithiophene-4, 5-dionesHydrogen spectrum ( 1 HNMR)(400MHz，CDCl 3 ，ppm)；
FIG. 4 ligand 2, 7-dibromo-4, 5-dibutoxy- [2,1-b:3,4-b 'synthesized by inventive example']Nuclear magnetic resonance hydrogen spectrum of dithiophene (f: 1 HNMR)(400MHz，DMSO-d 6 ，ppm)；
FIG. 5 NMR spectra of ligand 5-formyl-8-hydroxyquinoline synthesized in accordance with the example of the invention: ( 1 HNMR)(400MHz，CDCl 3 ，ppm)；
FIG. 6 NMR spectra of ligand 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid synthesized in accordance with an embodiment of the invention: ( 1 HNMR)(400MHz，CDCl 3 ，ppm)；
FIG. 7 is an example of an infrared spectrum (FTIR) (KBr, cm) of BET-Zn, BET-Cu, and BET-Ni of the synthesized metal complexes -1 )；
FIG. 8 Infrared Spectroscopy (FT-IR) (KBr, cm) of polymeric complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni synthesized according to an example of the invention -1 )；
FIG. 9 thermogravimetric analysis curves (TGA) (N) of polymeric complexes BBDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni synthesized according to an example of the invention 2 ，20℃/min)；
FIG. 10 is a graph of current density versus voltage (J-V) of dye-sensitized solar cells using BDTT-BET-Zn, BDTT-BET-Cu, and BDTT-BET-Ni, which are polymeric complexes synthesized according to examples of the present invention, as dye sensitizers;
FIG. 11 is an external quantum efficiency (IPCE) curve of BDTT-BET-Zn, BDTT-BET-Cu, and BDTT-BET-Ni polymeric complexes synthesized by an example of the present invention;
Detailed Description
The reaction synthesis route of the polymeric complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni comprises the following steps:
Figure BDA0003680727880000081
the invention will now be further illustrated by reference to specific examples
Example 1:
three new copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands have the following molecular structural formulas:
the preparation of the above polymeric complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni:
preparation of 1, 2-dithiophene-1, 2-dione: 3.6g (30mmol) of thiophene-3-carbaldehyde, K 2 CO 3 6.18 g (45mmol), 16mL of DMSO and 0.153g (30mol) of 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide were added to 50mL of mono
Figure BDA0003680727880000091
Heating to 60 ℃ in a flask with a mouth, reacting for 36h in the atmosphere of carbon dioxide, cooling to room temperature after the reaction is finished, adding 100mL of water, extracting with 50mL of anhydrous ether for three times, collecting an organic phase, adding anhydrous magnesium sulfate, drying for 12h, filtering, and spin-drying to obtain a light yellow liquid crude product, drying the crude product completely, and performing column chromatography by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 12 as an eluent to obtain 1.62g of golden yellow needle-shaped solid, wherein the yield is 73%, and m.p.94.1-94.7 ℃; FT-IR (KBr, cm) -1 ):3440cm -1 (-OH),3110cm -1 (＝C-H),1680cm -1 (C＝O),1160cm -1 (C-C),1500cm -1 (C＝C),1100cm -1 (C-S),700cm -1 (＝C-H)； 1 H-NMR(CDCl 3 ,ppm):8.35-8.36(d,1H),7.69-7.71(d,1H),7.39-7.41(q,1H)； 13 C-NMR(CDCl 3 ,ppm):186.81,137.59,137.50,127.54,126.96；
B. Benzo [1,2-b: 6,5-b']Preparation of dithiophene-4, 5-dione: 150mL of methylene chloride and 2.22g (10mmol) of 1, 2-dithiophene-1, 2-dione were added to a 250mL one-neck flask and stirred for 5min, then FeCl was slowly added 3 8.1 g (50mmol), 24h at 45 ℃, standing for 1h after the reaction is finished, adding 300ml of water, extracting with dichloromethane for three times, collecting an organic phase, drying for 24h with anhydrous magnesium sulfate, filtering, spin-drying to obtain a black flocculent solid, and eluting the obtained crude product with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 12 as an eluentColumn separation to obtain black needle solid 1.76g, yield 80%, m.p.289.1-289.6 deg.C; FT-IR (KBr, cm) -1 ):3090cm -1 (＝C-H),2930cm -1 ,2850cm -1 ,1390cm -1 ,1280cm -1 (-C-H),1660(C＝O),1510cm -1 (C＝C),1100cm -1 (C-S),885cm -1 (C-C),727cm -1 (＝C-H)； 1 H-NMR(CDCl 3 ,ppm):7.50(d,1H,＝CH),7.20(d,1H,＝CH)； 13 C-NMR(CDCl 3 ,ppm):174.62,143.96,135.11,127.88,125.66；
2, 7-dibromobenzo [1,2-b: 6,5-b']Preparation of dithiophene-4, 5-dione: reacting benzo [1,2-b: 6,5-b']Adding 4.40g (20mmol) of dithiophene-4, 5-dione, 3.738g (42mmol) of NBS and 100mL of DMF into a 250mL single-neck flask, heating to 70 ℃ for reaction for 24h, cooling to room temperature after the reaction is finished, pouring into 400mL of water, standing for 30min to completely separate out a solid, filtering by suction, and drying for 48h to obtain 2.85g of light blue solid, wherein the yield is 75.3 percent, and the m.p.204.3-204.9 ℃; FT-IR (KBr, cm) -1 ):3450cm -1 (-OH),30110cm -1 (＝CH),2930cm -1 ,2850cm -1 ,1410cm -1 ,1280cm -1 (-C-H),1680cm -1 (C＝O),1510cm -1 (C＝C),1080cm -1 (C-S),629cm -1 (C-Br)； 1 H-NMR(CDCl 3 ,ppm):7.47(s,1H,＝CH)； 13 C-NMR(CDCl 3 ,ppm):172.57,143.63,135.37,130.03,114.65；
2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b']Preparation of bithiophene (4): reacting 2, 7-dibromobenzo [1,2-b: 6,5-b']1.50g (4mmol) of dithiophene-4, 5-dione, 0.58g (4.2mmol) of n-bromoethane, 0.87g (2.7mmol) of tetrabutylammonium bromide and 4.44g (25.5mmol) of sodium hydrosulfite are added into a 100mL three-neck flask, a mixed solution of 20mL tetrahydrofuran and 10mL water is added, 10mL of KOH (2.31g) aqueous solution is slowly dripped through a constant-pressure dropping funnel under the protection of nitrogen, the temperature is slowly raised to 80 ℃ after the dripping is finished for reaction for 48 hours, the temperature is cooled to room temperature after the reaction is finished, 30mL ethyl acetate is used for extraction for three times, an organic phase is collected and dried over night by anhydrous magnesium sulfate, a light yellow liquid crude product is obtained after filtration and spin drying, and the obtained crude product is mixed with ethyl acetate and petroleum ether in a volume ratio of 1: 40The solution is used as eluent to carry out column separation, 0.84g of yellow liquid product is obtained, the yield is 43 percent, 1 H-NMR(CDCl 3 ,ppm):7.43(s,1H),4.10-4.13(t,2H),1.01-0.97(t,3H). 13 C-NMR(CDCl 3 ,ppm):142.78,134.15,129.02,124.66,112.84,74.13,13.97.FT-IR(KBr,cm -1 ):3440(-OH),3090(＝CH),2960,1380(-CH 3 ),2930,2850(C-H),1460(-CH 2 ),1280,1060(＝C-O-C).
e.5-formyl-8-hydroxyquinoline preparation; in a 500ml three-necked flask, 20g (137.6mmol) of 8-hydroxyquinoline and 80ml of anhydrous ethanol were sequentially added, and then a mixture of the above components was slowly added through a constant pressure separatory funnel in a mass ratio of 1: 1 aqueous sodium hydroxide solution (NaOH 40g, H) 2 O40 mL), heated to 80 ℃ after complete dissolution, refluxed, and slowly added with 36g (304mmol) of CHCl through a constant pressure separatory funnel over 1h 3 Reacting for 24 hours after the dropwise adding is finished; after the reaction, 50ml of distilled water was added, the solvent was removed by distillation under reduced pressure, and after drying by spinning, the reaction mixture was neutralized with dilute hydrochloric acid (hydrochloric acid: water: 10: 1) to pH 7, at which time a large amount of brown solid appeared; carrying out suction filtration and vacuum drying to obtain a brown blocky object, grinding the solid to be powdery, continuously drying, washing with petroleum ether after complete drying, naturally cooling the washing liquid, separating out an orange solid, filtering the supernatant liquid solid, recrystallizing twice with absolute ethyl alcohol, and completely drying the obtained solid to obtain 3.0g of orange pink filamentous crystals, wherein the yield is 12.3%, and the m.p.171.8-172.9 ℃; FT-IR (KBr, cm) -1 ):3447cm -1 (-OH),2920cm -1 (C-H),1690cm -1 (C＝O),1576cm -1 (C＝C),1510cm -1 (C＝N)； 1 H-NMR(CDCl 3 ,ppm):10.15(s,1H),9.67(d,1H),8,87(d,1H),8.00(d,1H),7.67(q,1H),7.65(d,1H)； 13 C-NMR(CDCl 3 ,ppm):192.04,157.86,148.74,140.45,137.85,134.76,126.59,124.72,123.56,109.02；
Preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid: after 3.0g (17.3mmol) of 5-formyl-8-quinolinol and 2.22g (26.0mmol) of cyanoacetic acid were added in this order to a 500ml three-necked flask, 9ml of acetic acid and then 100ml of acetonitrile were added thereto, and the mixture was stirred until dissolved, and after dissolution, the mixture was slowly dissolvedSlowly adding 1ml of piperidine, reacting the system at 90 ℃ for 36h, after the reaction is finished, spin-drying the solvent, putting the system in a vacuum drying oven until the solvent is completely dried to obtain a yellow blocky crude product, grinding the crude product into powder, washing the solid with trichloromethane for three times, drying the solid, and recrystallizing the solid with ethanol for two times to obtain 2.0g of orange powder solid, wherein the yield is 59.1%, and the m.p.200-201 ℃; 1 H-NMR(DMSO-d 6 ppm) 8.96(s,1H),8.87(d,1H),8.62(d,1H),8.42(d,1H),7.71(q,1H),7.26(d,1H). the active hydrogens on the hydroxyl and carboxyl groups cannot be characterized in the nuclear magnetic hydrogen spectrum due to the formation of hydrogen bonds, but can bind FT-IR and 13 C-NMR characterization proves that the target product is successfully synthesized, and the results are as follows: FT-IR (KBr, cm) -1 ):3180cm -1 (-OH),2235cm -1 (C≡N),1896cm -1 (C＝O),1662cm -1 (C＝O),1613cm -1 (C＝C),1566cm -1 (C＝N)； 13 C-NMR(CDCl 3 ,ppm):164.17,159.12,150.04,149.44,138.68,132.58,131.15,128.71,123.93,118.86,117.26,112.16,102.93.
G. Preparation of zinc-containing complex (BET-Zn): 2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b 'was added in this order to a 50mL single-necked flask']0.25g (0.5mmol) of dithiophene, 0.12g (0.55mmol) of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid, 25mL of THF were dissolved at an elevated temperature to 40 ℃ and then 0.105g (0.55mmol) of Zn (CH) 3 COO) 2 ·2H 2 Dissolving O in 20mL of anhydrous methanol, slowly dropwise adding the dissolved O into a single-neck flask through a constant-pressure funnel, heating to 75 ℃ for reaction for 24 hours, cooling to room temperature after the reaction is finished, putting the obtained product into a refrigerator overnight to separate out solids, and washing the obtained product with water and anhydrous ethanol for three times respectively after filtering to obtain 0.242g of yellow solid with the yield of 56.7%; FT-IR (KBr, cm) -1 ):3439cm -1 (-OH),2933cm -1 ,2853cm -1 (C-H),2204cm -1 (C≡N),1620cm -1 (C＝C),1561cm -1 (C＝N),1102cm -1 (S-O-Zn),509cm -1 (S-Zn)；
H. Preparation of copper-containing Complex (BET-Cu): the synthesis method of the complex (BET-Cu) is the same as that of the complex (BET-Zn), and Zn (CH) 3 COO) 2 ·2H 2 Changing O to 0.105g (0.55mmol) Zn (CH) 3 COO) 2 ·2H 2 O, which gave 0.242g of a yellow solid after the same work-up, in 56.7% yield; FT-IR (KBr, cm) -1 ):3439cm -1 (-OH),2933cm -1 ,2853cm -1 (C-H),2204cm -1 (C≡N),1620cm -1 (C＝C),1561cm -1 (C＝N),1102cm -1 (S-O-Zn),509cm -1 (S-Zn)；
I. Preparation of a Nickel-containing Complex (BET-Ni): the synthesis method of the complex (BET-Ni) is the same as that of the complex (BET-Zn), and Zn (CH) 3 COO) 2 ·2H 2 Changing O to 0.107g (0.55mmol) Ni (CH) 3 COO) 2 ·4H 2 O, and the orange red solid obtained after the same aftertreatment is 0.242g, and the yield is 57.2%; FT-IR (KBr, cm) -1 ):3440cm -1 (-OH),2932cm -1 ,2853cm -1 (C-H),2209cm -1 (C≡N),1620cm -1 (C＝C),1563cm -1 (C＝N),1106cm -1 (S-O-Ni),513cm -1 (S-Ni)；
J. Synthesizing a polymeric metal complex BDTT-BET-Zn: a50 ml single-neck flask was charged with 0.213g (0.30mmol) of zinc complex BET-Zn and 2, 6-dibromo-4, 8-bis (5- (2-ethyloctyl) thiophen-2-yl) benzo [1,2-b:4,5-b']Dithiophene (BDTT) donor monomer 0.184g (0.25mmol), zinc powder 0.08g (1.25mmol), triphenylphosphine 0.13g (0.5mmol), bis (triphenylphosphine) nickel dichloride 0.16g (0.25mmol) and 2, 2' -bipyridine 0.004g (0.024mmol), then adding 15mL DMF, and refluxing under nitrogen for 48 h; filtering after the reaction is finished, fully washing with absolute ethyl alcohol and drying to obtain brown solid powder 0.213g, wherein the yield is 53.8%; FT-IR (KBr, cm) -1 ):3437cm -1 (-OH),2929cm -1 ,2850cm -1 (C-H),2200cm -1 (C≡N),1617cm -1 (C＝C),1560cm -1 (C＝N),1100cm -1 (S-O-Zn),505cm -1 (S-Zn)；Mn＝10.12×10 3 g/mol,PDI＝20.34；
K. And (3) synthesizing a polymeric metal complex BDTT-BET-Cu: synthesis method of Polymer (BDTT-BET-Cu) referring to the synthesis of BDTT-BET-Zn, the zinc complex BET-Zn required for the reaction was replaced by copper complex BET-Cu 0.213g (0.30mmol) and then phase-separatedReacted with 0.184g (0.25mmol) of donor BDTT under the same conditions, and after the same treatment, obtained 0.203g of dark brown solid powder with 51.3% yield; FT-IR (KBr, cm) -1 ):3440cm -1 (-OH),2930cm -1 ,2849cm -1 (C-H),2208cm -1 (C≡N),1615cm -1 (C＝C),1559cm -1 (C＝N),1101cm -1 (S-O-Cu),508cm -1 (S-Cu)；Mn＝10.09×10 3 g/mol,PDI＝1.97；
L, synthesis of a polymeric metal complex BDTT-BET-Ni: synthesis method of Polymer (BDTT-BET-Ni) referring to the synthesis of BDTT-BET-Zn, the zinc complex BET-Zn required for the reaction was replaced by nickel complex BET-Ni 0.212g (0.30mmol), and then reacted with donor BDTT 0.184g (0.25mmol) under the same conditions to obtain dark brown solid powder 0.217g with 55.2% yield after the same treatment; FT-IR (KBr, cm) -1 ):3439cm -1 (-OH)，2931cm -1 ，2851cm -1 (C-H),2206cm -1 (C≡N),1619cm -1 (C＝C),1562cm -1 (C＝N),1103cm -1 (S-O-Ni),509cm -1 (S-Ni)；Mn＝8.57×10 3 g/mol,PDI＝2.05。
Example 2:
thermogravimetric analysis (TGA) curves of three copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni with benzodithiophene derivatives as ligands are determined, and the method comprises the following steps: thermogravimetric analyzer of SDTQ600 at N 2 The test was carried out at a temperature rise rate of 20 ℃/min under protection, and the test results are shown in FIG. 9.
Example 3:
determination of molecular weight test results of polymeric Complex dye sensitizers BDTT-BET-Zn, BDTT-BET-Cu and Table 1 three copolymerization complexes with benzodithiophene derivatives as ligands
Figure BDA0003680727880000151
Molecular weight of BDTT-BET-Ni, method is Gel Permeation Chromatography (GPC): a water styragel column (103, 104,
Figure BDA0003680727880000152
) The column oven temperature was 80 ℃ and the flow rate was 1.00mL/min, using DMF as the mobile phase and polystyrene solution as the reference, and the test results are shown in Table 1.
Example 4:
photovoltaic performance test of three copolymerization complexes taking benzodithiophene derivatives as ligands
Current density-voltage (J-V) curve test light intensity of 100mW/cm simulated by xenon lamp as light source 2 Changing the voltage and recording the change value of the current along with the voltage through a Keithley 2400 digital source meter; external quantum efficiency (IPCE) test A light source was provided by an Oriel Cornerstone monochromator under short-circuit conditions, the wavelength interval was 10nm, and the effective working area of DSSCs was 0.25cm 2 (ii) a The performance parameters and the photoelectric conversion efficiency of three novel D-A' -Pi-A type copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands of the dye-sensitized solar cell are determined, the current density-voltage (J-V) curve of the cell is shown as figure 10, and the external quantum efficiency (IPCE) curve of the cell is shown as figure 11; table 2 shows the photovoltaic performance and photoelectric conversion efficiency test results.
Table 2 photovoltaic performance test results of three copolymerization complexes taking benzodithiophene derivatives as ligands
Figure BDA0003680727880000161

Claims (3)

1. Three new copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands have the following structural formulas:
Figure FDA0003680727870000011
2. the preparation method of three new copolymerization complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni taking benzodithiophene derivatives as ligands according to claim 1 comprises the following steps:
(1) preparation of 1, 2-bithiophene-1, 2-dione:
adding thiophene-3-formaldehyde and potassium carbonate into a single-neck flask according to the molar ratio of 1.0: 1.0-1.0: 3.0, then adding a solvent DMSO and 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide into the flask, heating to 60 ℃ in the atmosphere of carbon dioxide to react for 32-40 h, cooling to room temperature after the reaction is finished, extracting with anhydrous ether for three times, collecting an organic phase, adding anhydrous magnesium sulfate, drying for 10-14 h, filtering, and spin-drying to obtain a crude product, drying the crude product completely, and performing column separation by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 10-1: 14 as an eluent to obtain a golden yellow acicular solid 1, 2-dithiophene-1, 2-dione;
(2) benzo [1,2-b: preparation of 6,5-b' ] dithiophene-4, 5-dione:
sequentially adding dichloromethane and 1, 2-dithiophene-1, 2-diketone into a single-neck flask, then slowly adding FeCl3, stirring for 20-26 h, wherein the molar ratio of the 1, 2-dithiophene-1, 2-diketone to FeCl3 is 1: 4-1: and 6, after the reaction is finished, standing, adding a proper amount of water, extracting with a proper amount of dichloromethane, collecting an organic phase, drying for 20-28 hours by using anhydrous magnesium sulfate, filtering, and then carrying out spin-drying to obtain a crude product, carrying out column separation on the crude product by using a mixed solution of ethyl acetate and petroleum ether as an eluent in a volume ratio of 1: 10-1: 14 to obtain black acicular solid benzo [1,2-b: 6,5-b' ] dithiophene-4, 5-dione;
(3)2, 7-dibromobenzo [1,2-b: preparation of 6,5-b' ] dithiophene-4, 5-dione:
in a single-neck flask, benzo [1,2-b: 6,5-b' ] dithiophene-4, 5-dione, NBS and DMF, benzo [1,2-b: the molar ratio of 6,5-b' ] dithiophene-4, 5-dione to NBS is 1: 1-1: and 3, heating to 70 ℃ for reaction for 20-28 h, cooling to room temperature after the reaction is finished, standing to enable the solid to be completely separated out, and drying after suction filtration to obtain a light blue solid 2, 7-dibromobenzo [1,2-b: 6,5-b' ] dithiophene-4, 5-dione;
(4) preparation of 2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b' ] -dithiophene:
mixing the components in a molar ratio of 1.0: 1.0: 0.5: 6.2-1.0: 1.2: 0.7: 6.4 2, 7-dibromobenzo [1,2-b: adding 6,5-b '] dithiophene-4, 5-dione, n-bromoethane, tetrabutyl ammonium bromide and sodium hydrosulfite into a three-neck flask, adding tetrahydrofuran aqueous solution, slowly dropwise adding KOH aqueous solution through a constant-pressure dropping funnel under the protection of nitrogen, slowly heating to 80 ℃ after dropwise adding, reacting for 44-52 h, cooling to room temperature after reaction, extracting with ethyl acetate, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, and spin-drying to obtain a light yellow crude liquid product, and performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether as an eluent in a volume ratio of 1: 30-1: 50 to obtain a yellow liquid product 2, 7-dibromo-4, 5-dibutoxy- [2,1-b:3,4-b' ] -dithiophene;
(5) preparation of 5-formyl-8-hydroxyquinoline:
adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-necked flask, adding a sodium hydroxide solution through a constant-pressure separating funnel under the stirring state, heating to 80 ℃ for reflux after complete dissolution, slowly adding chloroform through the constant-pressure separating funnel, wherein the molar ratio of the 8-hydroxyquinoline to the chloroform is 1.0: 2.0-1.0: 3.0, continuously reacting for 20-28 h, cooling to room temperature, removing the solvent by using a rotary evaporator, pouring the product into distilled water, adjusting the pH to be about 7, generating a large amount of brown solid at the moment, performing suction filtration to obtain the brown solid, obtaining a brown block-shaped object after complete vacuum drying, grinding to obtain a powdery solid, continuously drying, washing with petroleum ether after complete drying, naturally cooling the washing liquid overnight to separate out an orange solid, recrystallizing the remaining solid twice with absolute ethyl alcohol after filtering the supernatant, completely drying the obtained solid, obtaining orange pink filiform crystal 5-formyl-8-hydroxyquinoline;
(6) 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 and a small amount of acetic acid, stirring to dissolve the acetonitrile and the small amount of acetic acid, adding a small amount of piperidine, heating a system to 90 ℃, reacting for 32-40 h, closing the reaction, spin-drying the solvent, putting the system into a vacuum drying oven until the solvent is completely dried to obtain a yellow blocky crude product, grinding the crude product into powder, washing the solid with trichloromethane for three times, drying the solid, and recrystallizing the solid with ethanol for two times to obtain orange solid powder 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;
(7) preparation of metal complex BET-Zn:
taking the molar ratio of 1.0: 1.0-1.0: 2, 7-dibromo-4, 5-diethoxy- [2,1-b:3,4-b 'of 0']Adding bithiophene and 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid into a single-mouth bottle in sequence, heating to 40 ℃ to dissolve, and then adding Zn (CH) 3 COO) 2 ·2H 2 Dissolving O in anhydrous methanol, slowly dropwise adding the dissolved O through a constant-pressure funnel, heating to 75 ℃, reacting for 20-28 h, cooling to room temperature after the reaction is finished, putting the reaction product into a refrigerator overnight to completely separate out solids, filtering, washing with water for three times, and washing with anhydrous ethanol for three times to finally obtain a yellow solid zinc-containing complex BET-Zn;
(8) preparation of metal complex, BET-Cu and BET-Ni:
the synthesis method of the complex (BET-Cu, BET-Ni) is the same as that of the complex (BET-Zn), and Zn (CH) 3 COO) 2 ·2H 2 Changing O to Cu (CH) respectively 3 COO) 2 ·2H 2 O、Ni(CH 3 COO) 2 ·4H 2 O, respectively synthesizing to obtain a brown solid copper-containing complex BET-Cu and an orange-red solid nickel-containing complex BET-Ni;
(9) preparation of polymeric Metal Complex BDTT-BET-Zn:
taking the molar ratio of 1.0: 0.9 to 1.0: adding a complex monomer (BET-Zn) and 2, 6-dibromo-4, 8-di (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b '] dithiophene (BDTT) into a single-neck flask, then adding zinc powder, triphenylphosphine, bis (triphenylphosphine) nickel dichloride and 2, 2' -bipyridine, then adding DMF, carrying out reflux reaction for 44-52 h under the protection of nitrogen, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying to obtain a brown solid powdery complex product BDTT-BET-Zn;
(10) synthesizing a polymeric metal complex BDTT-BET-Cu and BDTT-BET-Ni;
according to the synthesis method of the polymers (BDTT-BET-Cu and BDTT-BET-Ni), referring to the synthesis of BDTT-BET-Zn, zinc metal complexes (BET-Zn) required by the reaction are respectively changed into metal complexes BET-Cu and BET-Ni, and the dark brown solid powder polymerization complexes BDTT-BET-Cu and BDTT-BET-Ni are respectively synthesized.
3. The use of three novel benzodithiophene derivative-coordinated co-complexes BDTT-BET-Zn, BDTT-BET-Cu and BDTT-BET-Ni according to claim 1 as dye sensitizers in dye-sensitized solar cells.
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CN115340665A (en) * 2022-09-20 2022-11-15 湘潭大学 Two butoxy benzodithiophene derivative mercury and cadmium copolymerization complexes, preparation method and application thereof
CN115466376A (en) * 2022-09-16 2022-12-13 湘潭大学 Two polymerization complexes taking imidazolyl benzodithiophene derivative as ligand, and preparation method and application thereof
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CN115466376A (en) * 2022-09-16 2022-12-13 湘潭大学 Two polymerization complexes taking imidazolyl benzodithiophene derivative as ligand, and preparation method and application thereof
CN115466403A (en) * 2022-09-16 2022-12-13 湘潭大学 Mercury and cadmium homopolymerization complex of two butoxy benzodithiophene derivatives and preparation method and application thereof
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Application publication date: 20220830