CN115466403A - Mercury and cadmium homopolymerization complex of two butoxy benzodithiophene derivatives and preparation method and application thereof - Google Patents
Mercury and cadmium homopolymerization complex of two butoxy benzodithiophene derivatives and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- -1 butoxy benzodithiophene derivatives Chemical class 0.000 title claims description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910052753 mercury Inorganic materials 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000012043 crude product Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- FESZEJDODWWDCC-UHFFFAOYSA-N 2-cyano-3-(8-hydroxyquinolin-5-yl)prop-2-enoic acid Chemical compound C(#N)C(C(=O)O)=CC1=C2C=CC=NC2=C(C=C1)O FESZEJDODWWDCC-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229960001701 chloroform Drugs 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- LIADJWREMDHKHQ-UHFFFAOYSA-N 8-hydroxyquinoline-5-carbaldehyde Chemical compound C1=CN=C2C(O)=CC=C(C=O)C2=C1 LIADJWREMDHKHQ-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 6
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- HRKPZDPFRDQSKZ-UHFFFAOYSA-N thieno[3,2-g][1]benzothiole-4,5-dione Chemical compound C1=2SC=CC=2C(=O)C(=O)C2=C1SC=C2 HRKPZDPFRDQSKZ-UHFFFAOYSA-N 0.000 claims description 6
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 5
- LKBSNQXXSMCHSS-UHFFFAOYSA-N 2,7-dibromothieno[3,2-g][1]benzothiole-4,5-dione Chemical compound C1=2SC(Br)=CC=2C(=O)C(=O)C2=C1SC(Br)=C2 LKBSNQXXSMCHSS-UHFFFAOYSA-N 0.000 claims description 5
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229960003540 oxyquinoline Drugs 0.000 claims description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001308 synthesis method Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- UMJPGEPKNLGAPW-UHFFFAOYSA-M 2-(3-benzyl-4-methyl-1,3-thiazol-3-ium-5-yl)ethanol;bromide Chemical compound [Br-].CC1=C(CCO)SC=[N+]1CC1=CC=CC=C1 UMJPGEPKNLGAPW-UHFFFAOYSA-M 0.000 claims description 3
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 claims description 2
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract description 4
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007341 Heck reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000011161 development Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 17
- 239000000975 dye Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 125000006416 CBr Chemical group BrC* 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
- H01G9/2063—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution comprising a mixture of two or more dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention relates to two butoxybenzodithiophene derivative mercury, cadmium homo-polymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd shown in a formula 1, a preparation method thereof and application of the compounds as dye sensitizers in dye-sensitized solar cells, wherein the dye sensitizers of the polymerization complexes are prepared from 4,5-dibutoxy-2,7-divinyl benzene [2,1-b:3,4-b']The dye-sensitized solar cell experiment based on the homopolymerization complex dye sensitizer shows good effects in the photovoltaic performance test of the dye-sensitized solar cell, which is characterized in that bithiophene is used as a main ligand and is coordinated with metal to form a metal complex as an auxiliary electron receptor A ', benzodithiophene Bithiophene (BDTT) is used as an electron donor D, and a Heck reaction is carried out to synthesize a D-A' -pi-A type homopolymerization complex: the photoelectric conversion efficiency reaches 12.89 percent and 11.23 percent respectively, the thermal decomposition temperature is more than 260 ℃, the thermal stability is good, and the method is to be used in the development of dye-sensitized solar cellsThe application aspect has certain prospect;
。
Description
Technical Field
The invention relates to two butoxy benzodithiophene derivative mercuric and cadmium homo-polymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd, a preparation method thereof and application of the BDTT-VBT-Cd as a dye sensitizer, is research and development and application of a photoelectric sensitization material in dye-sensitized solar cells (DSSCs), and belongs to the field of photoelectric materials in new materials.
Background
Compared with the traditional silicon solar cell, the dye-sensitized solar cell (DSSCs) has low cost of raw materials and is insensitive to the light receiving angle in the working process, so that the DSSCs are solar photoelectric conversion devices with very good application prospects, and the dye sensitizer is used as an important component of the DSSCs, so that the research and development of a plurality of scientific workers are obtained; in order to continuously improve the photovoltaic performance of the dye sensitizer, the original D-A structure is developed into the D-Pi-A structure, and the D-A' -Pi-A structure which is popular nowadays is developed; for a D-A '-Pi-A structure, an auxiliary electron receptor A' is introduced on the basis of the D-Pi-A structure to increase the partial electron withdrawing capability of the electron receptor and reduce the electron recombination, so that DSSCs get a new breakthrough in the aspect of photoelectric conversion efficiency, and other photoelectric properties such as thermal stability of the DSSCs are effectively improved.
Disclosure of Invention
The invention aims to provide and prepare two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd to be used as a D-A' -pi-A type dye sensitizer in a dye-sensitized solar cell, wherein the polymerization complex takes the benzodithiophene derivative BDTT as an electron donor D, and takes 4,5-dibutoxy-2,7-divinyl benzene [2,1-b:3,4-b ' ] dithiophene is coordinated with metal to form a complex which is an auxiliary acceptor A ', 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid is used as a pi bridge and an anchoring group, an electron donor D and an electron acceptor part (-A ' -pi-A) are polymerized through Heck coupling reaction to form the two metal complex dye sensitizers, the complex has good photoelectric conversion efficiency and thermal stability, the photoelectric conversion efficiency of the dye sensitized solar cell based on the two complexes as the dye sensitizers is 12.89% and 11.23% in sequence, and the structural general formula is as follows:
the preparation method of two butoxybenzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd comprises the following steps:
(1) Preparation of 1,2-dithienyl-1,2-dione:
reacting thiophene-3-carbaldehyde with K 2 CO 3 Adding DMSO and 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide into a single-neck flask according to the mol ratio of 1.0: 1.2-1.0: 1.8, heating and refluxing for 34-38 hours in the atmosphere of carbon dioxide, cooling to room temperature after the reaction is finished, adding water, extracting with diethyl ether for three times, adding anhydrous magnesium sulfate for drying, filtering and spin-drying to obtain a light yellow liquid, and performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 10-1: 15 as an eluent to obtain a golden yellow needle-shaped solid 1,2-dithiophene-1,2-diketone;
(2) Benzo [1,2-b:6,5-b' ] dithiophene-4,5-dione preparation:
methylene dichloride and 1,2-dithiophene-1,2-dione are added into a single-neck flask and stirred to be dissolved, and then FeCl is slowly added 3 Reacting at 45 ℃ for 22-26 h, standing for 1-2 h after the reaction is finished, adding deionized water, extracting with dichloromethane for three times, collecting the organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying to obtain black flocculent solid, 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: 10-1: 15 to obtain black acicular solid benzo [1,2-b:6,5-b']Dithiophene-4,5-dione;
(3) 2,7-dibromobenzo [1,2-b:6,5-b' ] dithiophene-4,5-dione preparation:
mixing benzo [1,2-b:6,5-b' ] dithiophene-4,5-dione and NBS are added into a single-neck flask according to the molar ratio of 1.0: 1.8-1.0: 2.4, DMF is added, then reaction is carried out for 2-26 h at 70 ℃, after the reaction is finished, the mixture is cooled to room temperature, poured into water and kept stand for 30-60 min, and after suction filtration and drying, light blue solid 2,7-dibromobenzo [1,2-b is obtained: 6,5-b' ] dithiophene-4,5-dione;
(4) 2,7-divinylbenzo [2,1-b: preparation of 3,4-b' ] dithiophene:
in a single-neck flask, 2,7-dibromobenzo [1,2-b:6,5-b '] dithiophene-4,5-dione and potassium vinyltrifluoroborate, adding cesium carbonate, 2-dicyclohexylphosphorus-2', 6 '-diisopropoxy-1,1' -biphenyl and palladium chloride, then slowly adding a tetrahydrofuran solution dropwise, heating and refluxing for 22-26 h under the protection of nitrogen, cooling to room temperature after the reaction is finished, removing excess solvent by reduced pressure distillation, pouring into water and extracting with ethyl acetate for three times, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying, performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether with a volume ratio of 1: 10-1: 14 as an eluent to obtain a black solid 2,7-divinylbenzo [2,1-b:3,4-b' ] dithiophene;
(5) 4,5-dibutoxy-2,7-divinylbenzo [2,1-b: preparation of 3,4-b' ] dithiophene:
2,7-divinylbenzo [2,1-b:3,4-b' ] dithiophene and n-bromobutane are added into a three-neck flask according to the molar ratio of 1.0: 0.8-1.0: 1.2, tetrabutylammonium bromide, sodium hydrosulfite and tetrahydrofuran solution are added, KOH solution is slowly dripped through a constant pressure dropping funnel under the protection of nitrogen, after the dripping is finished, the mixture reacts at 80 ℃ for 46-50 h, the mixture is cooled to room temperature after the reaction is finished, ethyl acetate is used for extraction for three times, organic phase is collected and dried by anhydrous magnesium sulfate, a yellowish liquid crude product is obtained after filtration and spin drying, the obtained crude product is subjected to column separation by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 36-1: 44 as an eluent, and a yellow liquid 4,5-dibutoxy-2,7-divinyl benzene [2,1-b:3,4-b' ] dithiophene;
(6) Preparation of 5-formyl-8-quinolinol:
adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-neck 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: 2.4, reacting for 22-26 hours, removing the ethyl alcohol and the chloroform through reduced pressure distillation after the reaction is finished, pouring distilled water, neutralizing with dilute hydrochloric acid until the pH value is 7.0, performing suction filtration to obtain a brown solid, performing vacuum drying to obtain a brown blocky object, grinding to be powdery, continuously drying, washing with petroleum ether, cooling a washing solution, recrystallizing the remaining solid with absolute ethyl alcohol twice after filtering a supernatant, and drying to obtain an orange pink filamentous crystal 5-formyl-8-hydroxyquinoline;
(7) Preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid:
adding 5-formyl-8-hydroxyquinoline and cyanoacetic acid into a three-necked flask according to the molar ratio of 1.0: 1.2-1.0: 1.8, adding acetic acid and acetonitrile, stirring until the acetic acid and the acetonitrile are dissolved, adding piperidine after the acetic acid and the acetonitrile are dissolved, reacting at 90 ℃ for 34-38 hours, after the reaction is finished, spin-drying the solvent and drying, grinding the solid into powder, washing the powder with trichloromethane for three times, drying the solid, and recrystallizing the solid with ethanol for two times to obtain orange powder 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;
(8) Preparing a metal complex VBT-Hg:
a three-necked flask was charged with 4,5-dibutoxy-2,7-divinylbenzo [2,1-b:3,4-b']Dithiophene and 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid, THF was then added, followed by dissolution at 40 ℃ and HgCl 2 Dissolving in absolute methanol, slowly dropwise adding through a constant-pressure funnel, reacting at 75 ℃ for 22-26 h, cooling to room temperature after the reaction is finished, putting into a refrigerator for overnight, filtering, washing with water for three times and absolute ethyl alcohol for three times respectively, and finally obtaining a light yellow solid Hg complex VBT-Hg;
(9) Preparing a metal complex VBT-Cd:
the synthesis method of the complex VBT-Cd is the same as that of VBT-Hg, and HgCl is added 2 By Cd (CH) 3 COO) 2 ·2H 2 O, finally obtaining a golden yellow solid Cd-containing complex VBT-Cd;
(10) Preparation of polymer complex BDTT-VBT-Hg:
adding Hg-containing complexes VBT-Hg and 2,6-dibromo-4,8-bis (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b '] dithiophene (BDTT) with the molar ratio of 1.0: 0.8-1.0: 1.2 into a single-neck flask, then sequentially adding zinc powder, triphenylphosphine, delta bis (triphenylphosphine) nickel dichloride, 2,2' -bipyridine and DMF, refluxing VBck for 46-50 h under the protection of nitrogen according to a HeHex polymerization reaction, after the reaction is finished, filtering, fully washing with anhydrous ethanol, and drying to obtain a brownish green solid polymerization complex BDTT-T-Hg;
(11) Preparing a polymerization complex BDTT-VBT-Cd:
the synthesis method of the polymer complex BDTT-VBT-Cd is the same as that of the BDTT-VBT-Hg, and the Hg-containing complex VBT-Hg is replaced by the metal complex VBT-Cd to finally obtain the deep brown solid polymer complex BDTT-VBT-Cd;
the applications of two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd are as follows: 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 two butoxy benzodithiophene derivative mercury and cadmium homopolymerization complexes, wherein the polymerization complex takes a Benzodithiophene Derivative (BDTT) with strong electron donating capability as a donor D, and takes 4,5-dibutoxy-2,7-divinyl benzene [2,1-b:3,4-b ' ] dithiophene is coordinated with metal to form a complex as an auxiliary receptor A ', 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid is coordinated with metal to form a pi bridge, a receptor A and an anchoring group, and a donor and a complex receptor part-A ' -pi-A are connected through a Heck reaction to synthesize the complex, wherein the complex has good photoelectric conversion efficiency which is 12.89% and 11.23% respectively, and (2) the preparation method is simple and raw materials are easy to obtain; (3) Has good electrochemical performance, thermal performance and light stability, and the thermal decomposition temperature is over 260 ℃, thereby being beneficial to practical application.
Drawings
FIG. 1 NMR spectra of ligand 1,2-dithienyl-1,2-diketone synthesized in accordance with the example of the present invention (R) ((R)) 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 2 ligand benzo [1,2-b:6,5-b']NMR spectrum of dithiophene-4,5-dione ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 3 ligand 2,7-dibromobenzo [1,2-b:6,5-b']NMR spectrum of dithiophene-4,5-dione ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 4 example ligand 2,7-divinylbenzo [2,1-b:3,4-b']NMR spectrum of bithiophene ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 5 ligand 4,5-dibutoxy-2,7-divinylbenzo [2,1-b:3,4-b']NMR spectrum of bithiophene ( 1 H-NMR)(400MHz，CDCl 3 ， ppm)；
FIG. 6 NMR spectra of ligand 5-formyl-8-hydroxyquinoline synthesized in the example of the invention: ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 7 NMR spectra of ligand 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid synthesized in accordance with an embodiment of the invention: ( 1 H-NMR)(400MHz，CDCl 3 ，ppm)；
FIG. 8 Infrared Spectrum (FT-IR) (KBr, cm) of VBT-Hg and VBT-Cd metal complexes synthesized by the example of the invention -1 )；
FIG. 9 Infrared Spectroscopy (FT-IR) (KBr, cm) of polymeric complexes BDTT-VBT-Hg and BDTT-VBT-Cd synthesized by the example of the invention -1 )；
FIG. 10 thermogravimetric analysis curves (TGA) (N) of polymeric complexes BDTT-VBT-Hg, BDTT-VBT-Cd synthesized by the examples of the present invention 2 ，20℃/min)；
FIG. 11 is a current density-voltage (J-V) curve of a dye-sensitized solar cell using the polymer complexes BDTT-VBT-Hg and BDTT-VBT-Cd synthesized by the example of the present invention as dye sensitizers;
FIG. 12 is a graph of external quantum efficiency (IPCE) of dye-sensitized solar cells using BDTT-VBT-Hg and BDTT-VBT-Cd as dye sensitizers synthesized according to the example of the present invention.
Detailed Description
The reaction synthetic route of two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd is shown as formula 1:
The invention will now be further illustrated by reference to specific examples
Example 1:
the molecular structural formula of two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd is shown as a formula 2:
molecular structural formula of two polymers in formula 2
The preparation of the two butoxybenzodithiophene derivatives mercury and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd:
preparation of 1, 2-dithiophene-1,2-dione: 3.6g of thiophene-3-carbaldehyde (30 mmol), 6.18g K 2 CO 3 (45 mmol), 16mL of DMSO and 0.153g of 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide were added to a 50mL single-neck flask, the mixture was heated to 60 ℃ in an atmosphere of carbon dioxide and reacted for 36 hours, after completion of the reaction, the mixture was cooled to room temperature, 100mL of water was added, extraction was carried out three times with 50mL of anhydrous ether, and the organic phase was collectedAdding anhydrous magnesium sulfate for drying, filtering and spin-drying to obtain a light yellow liquid, and performing column chromatography on the obtained crude product by using ethyl acetate and petroleum ether as eluents according to the volume ratio of 1; 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), nuclear magnetic resonance hydrogen spectrum: (C-H) 1 H-NMR) is shown in figure 1, 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 of 1, 2-dithiophene-1,2-dione (10 mmol) were added to a 250mL single-neck flask and stirred for 5min, then 8.1g of FeCl was slowly added 3 (50 mmol), reacting at 45 ℃ for 24h, standing for 1h after the reaction is finished, adding 300ml of water, extracting with dichloromethane for three times, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, and then spin-drying to obtain a black flocculent solid, and performing column separation on the obtained crude product by using ethyl acetate and petroleum ether as eluents according to a volume ratio of 1; FT-IR (KBr, cm) -1 ):3090cm -1 (＝C-H),2930cm -1 ,2850cm -1 ,1390cm -1 , 1280cm -1 (-C-H),1660cm -1 (C＝O),1510cm -1 (C＝C),1100cm -1 (C-S), 885cm -1 (C-C),727cm -1 (= C-H), nuclear magnetic resonance hydrogen spectrum: (C-H) 1 H-NMR) is shown in figure 2, 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；
c.2, 7-dibromobenzo [1,2-b:6,5-b']Preparation of dithiophene-4,5-dione: 4.40g of benzo [1,2-b:6,5-b']Adding dithiophene-4,5-diketone (20 mmol), 3.738g NBS (42 mmol) and 100mL 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 water, standing30min, and drying after suction filtration to obtain light blue solid 2.85g with a yield of 75.3%; m.p.204.3-204.9 deg.C, 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),1080 cm -1 (C-S),629cm -1 (C-Br), nuclear magnetic resonance hydrogen spectrum (C-Br) 1 H-NMR) is shown in figure 3, 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-Divinylbenzo [2,1-b:3,4-b']Preparation of dithiophene: a50 mL one-neck flask was charged with 0.378g of 2, 7-dibromobenzo [1,2-b:6,5-b']Dithiophene-4,5-dione (1 mmol), 0.978g cesium carbonate (3 mmol), 27.9mg 2-dicyclohexylphosphorus-2 ',6' -diisopropoxy-1,1 ' -biphenyl (0.06 mmol), 3.5mg palladium chloride (0.02 mmol), 0.281g potassium vinyltrifluoroborate (2.1 mmol), then 11ml tetrahydrofuran solution (tetrahydrofuran: water = 10: 1) was slowly added dropwise, the temperature was slowly raised to 85 ℃ under the protection of nitrogen for reaction for 24h, after the reaction was completed, the solution was cooled to room temperature, after spin-drying, poured into water and extracted with ethyl acetate three times, the organic phase was collected and dried over anhydrous magnesium sulfate, after filtration, spin-drying, the crude product was subjected to column chromatography with petroleum ether and ethyl acetate as eluents at a volume ratio of 12; nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) is shown in figure 4, 1 H-NMR(CDCl 3 ,ppm):7.32(s,1H),6.71-6.78(q,1H), 5.61-5.66(d,1H),5.33-5.36(d,1H)； 13 C-NMR(CDCl 3 ,ppm):174.29, 143.45,142.17,135.56,128.55,125.36,116.73；FT-IR(KBr,cm -1 ):3430 cm -1 (-OH),3090cm -1 (＝C-H),2920cm -1 ,2850cm -1 (C-H),1650cm -1 (C＝O),1570cm -1 ,1500cm -1 (C＝C)；
e.4, 5-dibutoxy-2,7-divinylbenzo [2,1-b:3,4-b']Preparation of dithiophene: 1.08g of 2, 7-divinylbenzo [2,1-b:3,4-b']Dithiophene (4 mmol), 0.58g n-bromobutane (4.2 mmol), 0.87g tetrabutylammonium bromide (2.7 mm)ol), 4.44g sodium hydrosulfite (25.5 mmol) was added to a 100mL three-necked flask, 30mL tetrahydrofuran solution (tetrahydrofuran: water = 3: 2) was added, and KOH solution (KOH 2.3g, H) was slowly added dropwise through a constant pressure dropping funnel under protection of nitrogen gas 2 O10 mL), slowly raising the temperature to 80 ℃ after the dropwise addition is finished, reacting for 48 hours, cooling to room temperature after the reaction is finished, extracting with 30mL of ethyl acetate for three times, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, and spin-drying to obtain a light yellow liquid, and separating the crude product by using petroleum ether and ethyl acetate as eluents with a volume ratio of 40 1 H-NMR) is shown in figure 5, 1 H-NMR(CDCl 3 ,ppm):7.43(s,1H),4.10-4.13(t,2H),0.97-1.01 (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 ):3420cm -1 (-OH),2920cm -1 ,2850cm -1 (C-H),1640cm -1 (C＝C),1550cm -1 (C＝C),1460cm -1 (-CH 2 ),1380cm -1 (-CH 3 ),1270cm -1 (C-O-C)；
preparation of F.5-formyl-8-hydroxyquinoline: 20g (137.6 mmol) of 8-hydroxyquinoline are added in sequence to a 500ml three-necked flask, 80ml of absolute ethanol are added, and then a sodium hydroxide solution (NaOH 40g, H) with a mass ratio of 1:1 is slowly added through a constant pressure separatory funnel under stirring 2 O40 mL), heated to 80 ℃ after complete dissolution, refluxed, and slowly added with 36g (304 mmol) of CHCl over 1h through a constant pressure separatory funnel 3 After the dropwise addition, the reaction is carried out for 24 hours, after the reaction is finished, 50ml of distilled water is added, then ethanol and chloroform are removed through reduced pressure distillation, after the reaction is finished, the solution is poured into 500ml of distilled water, diluted hydrochloric acid (hydrochloric acid: water = 10: 1) is used for neutralizing until the pH value is 7, after the suction filtration, a brown block-shaped object is obtained through vacuum drying, after the brown block-shaped object is ground to be a powdery solid, the powdery solid is continuously dried, after the drying, the washing liquid is washed by petroleum ether, the washing liquid is naturally cooled overnight to separate out an orange solid, after the supernatant is filtered, the remaining solid is recrystallized twice by absolute ethyl alcohol, and the obtained solid is dried to obtain 3.0g of orange powdery filiform crystals, the yield is 12.3%, and 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); nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) is shown in figure 6, 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: adding 3.0g (17.3 mmol) of 5-formyl-8-hydroxyquinoline and 2.22g (26.0 mmol) of cyanoacetic acid into a 500ml three-neck flask in sequence, then adding 9ml of acetic acid, then adding 100ml of acetonitrile, stirring until the acetic acid and the acetonitrile are dissolved, slowly adding 1ml of piperidine after the dissolution, reacting the system at 90 ℃ to obtain 36h, after the reaction is finished, spin-drying the solvent, then placing the solvent in a vacuum drying oven for drying to obtain a yellow blocky crude product, grinding the crude product to be powder, washing the solid with trichloromethane three times, drying the solid, then recrystallizing the solid with ethanol twice to obtain 2.0g of orange powder, wherein the yield is 59.1%, and m.p.200-201 ℃; nuclear magnetic resonance hydrogen spectrum ( 1 H-NMR) is shown in figure 7, 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 combine FT-IR with 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；
H. Preparation of Hg-containing complex VBT-Hg: 0.193g of 4, 5-dibutoxy-2,7-divinylbenzo [2,1-b:3,4-b']Dithiophene (0.5 mmol), 0.12g 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid (0.55 mmol), 25mL THF were added to a 50mL one-neck flask, allowed to warm to 40 ℃ to dissolve, then 0.149g HgCl was added 2 (0.55mmol) is dissolved in 20mL of anhydrous methanol, slowly dropped through a constant pressure funnel, heated to 75 ℃ for reaction for 24h, cooled to room temperature after the reaction is finished, put into a refrigerator overnight to completely separate out the solid, filtered, washed with water for three times and absolute ethyl alcohol for three times to finally obtain a light yellow solid (0.256 g), the yield is 59.6%, an infrared spectrum (FT-IR) is shown in figure 8, the FT-IR (KBr, cm) is shown in the figure -1 ):3442(-OH),2932,2851(C-H),2200(C≡N),1615(C＝C),1561 (C＝N),1103(S-O-Hg),497(S-Hg)；
I. Preparing a Cd-containing complex VBT-Cd: the reaction is the same as the synthesis of VBT-Hg, hgCl 2 The reaction mixture was exchanged for 0.134g (0.55 mmol) of Cd (CH) 3 COO) 2· 2H 2 O, and the same post-treatment gives a golden yellow solid 0.225g, with a yield of 56.4%, an infrared spectrum (FT-IR) as shown in FIG. 8, FTIR (KBr, cm) -1 ):3441(-OH),2931,2851(C-H), 2203(C≡N),1613(C＝C),1563(C＝N),1102(S-O-Cd),498(S-Cd)；
J. Preparation of polymer complex BDTT-VBT-Hg: into a 50ml single-neck flask were charged 0.254g (0.30 mmol) of the above mercury complex VBT-Hg monomer and 2,6-dibromo-4,8-bis (5- (2-ethyloctyl) thiophen-2-yl) benzo [1,2-b:4,5-b']Adding 0.221g (0.30 mmol) of dithiophene (BDTT) donor monomer, 0.00425g (0.019 mmol) of catalyst palladium acetate (Pd (CH 3 COO) 2) and 0.0275g (0.09 mmol) of tri (2-tolyl) phosphine, adding 7mL of DMF and 3mL of dried triethylamine under the protection of inert gas, stirring for dissolving, heating and refluxing for 48h, cooling after the reaction stops, filtering, washing with absolute ethyl alcohol for a plurality of times, and drying in a vacuum drying oven to obtain 0.251g of brown-green solid powder with the yield of 58.6%, wherein an infrared spectrum (FT-IR) is shown in figure 9, FTIR (KBr, cm) is shown in the specification, and the mass ratio of the mixture is determined by the following steps of -1 ):3440 (-OH),2932,2850(C-H),2200(C≡N),1613(C＝C),1558(C＝N),1100 (S-O-Ni),494(S-Hg).Mn＝10.10×103g/mol,PDI＝1.84；
K. Preparing a polymerization complex BDTT-VBT-Cd: the synthesis method of the polymer is the same as that of BDTT-VBT-Hg, only Hg complex VBT-Hg needs to be changed into Cd complex VBT-Cd 0.254g (0.30 mmol), A dark brown solid powder 0.234g was obtained in 57.1% yield, and an infrared spectrum (FT-IR) as shown in FIG. 9, FTIR (KBr, cm) -1 ):3438 (-OH),2930,2851(C-H),2205(C≡N),1611(C＝C),1557(C＝N),1101 (S-O-Cd),495(S-Cd).Mn＝10.49×103g/mol,PDI＝1.89。
Example 2:
determining thermogravimetric analysis (TGA) curves of two butoxybenzodithiophene derivative mercuric, cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd, and adopting the following steps: thermogravimetric analyzer of SDTQ600, 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. 10.
Example 3:
the molecular weights of two butoxybenzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd are measured by a Gel Permeation Chromatography (GPC): a water styragel column (103, 104,
) The column oven temperature was 80 ℃, DMF was used as the mobile phase, polystyrene solution was used as the reference, and the flow rate was 1.00mL/min, and the test results are shown in table 1:
TABLE 1 molecular weight test of two butoxybenzodithiophene derivative mercuric, cadmium homo-complexes
Example 4:
the photovoltaic performance tests of two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd: current density-current (J-V) curve test light source is light intensity 100mW/cm simulated by xenon lamp 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, with a wavelength test interval of 10nm and an effective working area of DSSCs of 0.25cm, measured under short-circuit conditions 2 (ii) a Measuring performance parameters and photoelectric conversion of dye-sensitized solar cells using two polymeric complex dye sensitizers BDTT-VBT-Hg and BDTT-VBT-CdThe cell current density-voltage (J-V) curve is shown in figure 11, and the cell external quantum efficiency (IPCE) curve is shown in figure 12; table 2 is their photovoltaic performance and photoelectric conversion efficiency test results:
TABLE 2 photovoltaic Performance testing of two butoxybenzodithiophene derivative mercuric and cadmium homo-polymerization complexes
Claims (2)
1. The two butoxy benzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd have the following structural formulas:
the preparation method of the two butoxybenzodithiophene derivative mercuric and cadmium homopolymerization complexes BDTT-VBT-Hg and BDTT-VBT-Cd comprises the following steps:
(1) Preparation of 1,2-dithienyl-1,2-dione:
reacting thiophene-3-carbaldehyde with K 2 CO 3 Adding DMSO and 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide into a single-neck flask according to the mol ratio of 1.0: 1.2-1.0: 1.8, heating and refluxing for 34-38 hours in the atmosphere of carbon dioxide, cooling to room temperature after the reaction is finished, adding water, extracting with diethyl ether for three times, adding anhydrous magnesium sulfate for drying, filtering and spin-drying to obtain a light yellow liquid, and performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 10-1: 15 as an eluent to obtain a golden yellow needle-shaped solid 1,2-dithiophene-1,2-diketone;
(2) Benzo [1,2-b:6,5-b' ] dithiophene-4,5-dione preparation:
dichloromethane and 1,2-dithiophene-1,2-diketone are added into a single-neck flask and dissolved by stirring, and then FeCl is slowly added 3 Reacting at 45 ℃ for 22-26 h, and standing after the reaction is finishedPlacing for 1-2 h, adding deionized water, extracting for three times by using dichloromethane, collecting an organic phase, drying by using anhydrous magnesium sulfate, filtering, and then carrying out spin-drying to obtain a black flocculent solid, wherein the obtained crude product is subjected to column chromatography by using a mixed solution of ethyl acetate and petroleum ether as an eluent in a volume ratio of 1: 10-1: 15 to obtain black needle-shaped solid benzo [1,2-b:6,5-b']Dithiophene-4,5-dione;
(3) 2,7-dibromobenzo [1,2-b:6,5-b' ] dithiophene-4,5-dione preparation:
mixing benzo [1,2-b:6,5-b' ] dithiophene-4,5-dione and NBS are added into a single-neck flask according to the mol ratio of 1.0: 1.8-1.0: 2.4, DMF is added, then reaction is carried out for 22-26 h at 70 ℃, after the reaction is finished, the mixture is cooled to room temperature, poured into water and kept stand for 30-60 min, and after suction filtration and drying, light blue solid 2,7-dibromobenzo [1,2-b is obtained: 6,5-b' ] dithiophene-4,5-dione;
(4) 2,7-divinylbenzo [2,1-b: preparation of 3,4-b' ] dithiophene:
in a single-neck flask, 2,7-dibromobenzo [1,2-b:6,5-b '] dithiophene-4,5-dione and potassium vinyltrifluoroborate, adding cesium carbonate, 2-dicyclohexylphosphorus-2', 6 '-diisopropoxy-1,1' -biphenyl and palladium chloride, then slowly adding a tetrahydrofuran solution dropwise, heating and refluxing for 22-26 h under the protection of nitrogen, cooling to room temperature after the reaction is finished, removing excess solvent by reduced pressure distillation, pouring into water and extracting with ethyl acetate for three times, collecting an organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying, performing column separation on the obtained crude product by using a mixed solution of ethyl acetate and petroleum ether with a volume ratio of 1: 10-1: 14 as an eluent to obtain a black solid 2,7-divinylbenzo [2,1-b:3,4-b' ] dithiophene;
(5) 4,5-dibutoxy-2,7-divinylbenzo [2,1-b: preparation of 3,4-b' ] dithiophene:
2,7-divinylbenzo [2,1-b:3,4-b' ] dithiophene and n-bromobutane are added into a three-neck flask according to the molar ratio of 1.0: 0.8-1.0: 1.2, tetrabutylammonium bromide, sodium hydrosulfite and tetrahydrofuran solution are added, KOH solution is slowly dripped through a constant pressure dropping funnel under the protection of nitrogen, after the dripping is finished, the mixture reacts at 80 ℃ for 46-50 h, the mixture is cooled to room temperature after the reaction is finished, ethyl acetate is used for extraction for three times, organic phase is collected and dried by anhydrous magnesium sulfate, a yellowish liquid crude product is obtained after filtration and spin drying, the obtained crude product is subjected to column separation by using a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1: 36-1: 44 as an eluent, and a yellow liquid 4,5-dibutoxy-2,7-divinyl benzene [2,1-b:3,4-b' ] dithiophene;
(6) Preparation of 5-formyl-8-quinolinol:
adding 8-hydroxyquinoline and absolute ethyl alcohol into a three-neck 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: 2.4, reacting for 22-26 hours, removing the ethyl alcohol and the chloroform through reduced pressure distillation after the reaction is finished, pouring distilled water, neutralizing with dilute hydrochloric acid until the pH value is 7.0, performing suction filtration to obtain a brown solid, performing vacuum drying to obtain a brown blocky object, grinding to be powdery, continuously drying, washing with petroleum ether, cooling a washing solution, recrystallizing the remaining solid with absolute ethyl alcohol twice after filtering a supernatant, and drying to obtain an orange pink filamentous crystal 5-formyl-8-hydroxyquinoline;
(7) Preparation of 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid:
adding 5-formyl-8-hydroxyquinoline and cyanoacetic acid into a three-necked flask according to the molar ratio of 1.0: 1.2-1.0: 1.8, adding acetic acid and acetonitrile, stirring until the acetic acid and the acetonitrile are dissolved, adding piperidine after the acetic acid and the acetonitrile are dissolved, reacting at 90 ℃ for 34-38 hours, after the reaction is finished, spin-drying the solvent and drying, grinding the solid into powder, washing the powder with trichloromethane for three times, drying the solid, and recrystallizing the solid with ethanol for two times to obtain orange powder 2-cyano-3- (8-hydroxyquinoline-5-yl) acrylic acid;
(8) Preparing a metal complex VBT-Hg:
a three-necked flask was charged with 4,5-dibutoxy-2,7-divinylbenzo [2,1-b:3,4-b']Dithiophene and 2-cyano-3- (8-hydroxyquinolin-5-yl) acrylic acid, THF was then added, followed by dissolution at 40 ℃ and HgCl 2 Dissolving in anhydrous methanol, slowly dropwise adding through a constant-pressure funnel, reacting at 75 ℃ for 22-26 h, cooling to room temperature after the reaction is finished, putting into a refrigerator for overnight, filtering, washing with water for three times and washing with anhydrous ethanol for three times respectively to finally obtain a light yellow solid Hg-containing complex VBT-Hg;
(9) Preparing a metal complex VBT-Cd:
the synthesis method of the complex VBT-Cd is the same as that of VBT-Hg, and HgCl is added 2 To Cd (CH) 3 COO) 2 ·2H 2 O, finally obtaining a golden yellow solid Cd-containing complex VBT-Cd;
(10) Preparation of polymer complex BDTT-VBT-Hg:
adding Hg-containing complexes VBT-Hg and 2,6-dibromo-4,8-di (5- (2-ethyloctyl) thiophene-2-yl) benzo [1,2-b:4,5-b '] dithiophene (BDTT) with the molar ratio of 1.0: 0.8-1.0: 1.2 into a single-neck flask, sequentially adding zinc powder, triphenylphosphine, bis (triphenylphosphine) nickel dichloride, 2,2' -bipyridine and DMF, refluxing for 46-50 h under the protection of nitrogen according to Heck polymerization reaction, filtering after the reaction is finished, fully washing with absolute ethyl alcohol, and drying to obtain a brown green solid polymerization complex BDTT-VBT-Hg;
(11) Preparing a polymerization complex BDTT-VBT-Cd:
the synthesis method of the polymer complex BDTT-VBT-Cd is the same as that of the BDTT-VBT-Hg, and the Hg-containing complex VBT-Hg is replaced by the metal complex VBT-Cd to finally obtain the deep brown solid polymer complex BDTT-VBT-Cd.
2. The use of two butoxybenzodithiophene derivative mercuric, cadmium homo-complexes BDTT-VBT-Hg, BDTT-VBT-Cd according to claim 1 as dye sensitizers in dye sensitized solar cells.
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| US5837390A (en) * | 1995-05-10 | 1998-11-17 | Sony Corporation | Metal complex, method for producing the same and optical device |
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