CN112250843B - 四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物及其制备方法与用途 - Google Patents
四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物及其制备方法与用途 Download PDFInfo
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- CN112250843B CN112250843B CN202011108603.5A CN202011108603A CN112250843B CN 112250843 B CN112250843 B CN 112250843B CN 202011108603 A CN202011108603 A CN 202011108603A CN 112250843 B CN112250843 B CN 112250843B
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- -1 alkylated salicylaldehyde Schiff base Chemical class 0.000 title claims abstract description 36
- 239000002262 Schiff base Substances 0.000 title claims abstract description 24
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 40
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
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- 239000012043 crude product Substances 0.000 claims description 19
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
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- VJLVGOUBVJLEDT-UHFFFAOYSA-N 5-ethenyl-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=C)C=C1C=O VJLVGOUBVJLEDT-UHFFFAOYSA-N 0.000 claims description 11
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- WFACWTZLXIFJCM-UHFFFAOYSA-N 5-(chloromethyl)-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(CCl)C=C1C=O WFACWTZLXIFJCM-UHFFFAOYSA-N 0.000 claims description 9
- 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
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
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- 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 7
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- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
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- 238000001308 synthesis method Methods 0.000 claims description 5
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- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 3
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- 229960003540 oxyquinoline Drugs 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
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- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
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- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 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
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 8
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 abstract 1
- 238000007341 Heck reaction Methods 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
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- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 20
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- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 229910014291 N—Cu Inorganic materials 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明涉及式1所示的四种D‑A’‑(π‑A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT‑SBD‑Cd、BDTT‑SBD‑Zn、BDTT‑SBD‑Cu、BDTT‑SBD‑Ni及其制备方法与用途，它们是以烷基化的水杨醛席夫碱衍生物为主配体与金属配位形成的金属配合物为辅助电子配体A’，以苯并二噻吩联二噻吩(BDTT)做电子给体D，通过Heck反应合成的D‑A’‑(π‑A)2型聚合金属配合物，实验基于以BDTT‑SBD‑Cd、BDTT‑SBD‑Zn、BDTT‑SBD‑Cu、BDTT‑SBD‑Ni为染料敏化剂的染料敏化太阳能电池的光伏性能测试表现出较好的效果：光电转换效率分别为9.05％、8.21％、6.83％、6.26％，其热分解温度均达到了175℃以上，热稳定性良好，这将在染料敏化太阳能电池的发展应用方面具有一定的前景；
Description
技术领域
本发明涉及四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni及其制备方法与应用其为染料敏化太阳能电池(DSSCs)中作染料敏化剂的用途，是对染料敏化太阳能电池(DSSCs)中光电敏化材料的研发与应用，属于新材料中的光电材料领域。
背景技术
染料敏化太阳能电池以其相对较低的成本和较好的光伏性能而成为研究的热点，研究人员发现在D-π-A结构的基础上引入辅助电子配体A’的D-A’-π-A结构，增加一个辅助受体A’，可以达到降低电荷复合的目的，从而提高其光电流，进而得到一个更高的效率，相比纯有机染料，有机金属光敏剂由于金属离子的引入，大大改善了敏化剂光、热及化学稳定性，也能通过改变配位的金属原子调节染料分子的HOMO能级和LOMO能级，因金属配合物有很强的吸拉电子能力，并能通过调节配位键强度来调节吸电子能力，而达到染料分子优良的推拉电子平衡。本发明研究用金属配合物代替苯并噻二唑等有机化合物做D-A’-π-A型染料敏化剂的辅助受体A’，并通过聚合扩大分子共轭平面性，设计与制备了四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni，表现出较好的光伏性能。
发明内容
本发明的目的为提供和制备以苯并噻二吩联二噻吩衍生物BDTT为电子给体(D)，以烷基化的水杨醛席夫碱衍生物为主配体与金属配位形成的配合物为辅助电子受体(A’)，以2-氰基-3-(8-羟基喹啉-5-基)丙烯酸与金属配位形成π桥、受体(A)和锚定基团，通过Heck反应将给体(D)和配合物受体部分[-A’-(π-A)2]连接而合成的四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni，并应用作为染料敏化太阳能电池中的染料敏化剂，该类金属配合物具有良好的光电转换效率和热稳定性，基于以BBDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni为染料敏化剂的染料敏化太阳能电池的光电转化效率分别达到了9.05％、8.21％、6.83％、6.26％，其结构通式如下：
四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的制备方法：
(1))5-氯甲基水杨醛的制备：
称取多聚甲醛至三口瓶中，沿壁迟缓加入大量的浓盐酸，待搅拌均匀后，缓慢滴加水杨醛，多聚甲醛和水杨醛的摩尔比为1.8∶1.0～2.2∶1.0，室温搅拌反应36～72h，过滤得到粗产物白色固体，依次用饱和碳酸氢钠溶液和蒸馏水洗涤至中性后放置干燥箱干燥，粗产物用石油醚重结晶多次，得到白色针状固体5-氯甲基水杨醛；
(2)5-乙烯基水杨醛的制备：
取摩尔比为1∶9～11的5-氯甲基水杨醛和三苯基膦于三口烧瓶，加苯溶解，回流反应1h，冷却后过滤，所得固体用少量乙醚分三次洗涤，得白色粉末状固体，将固体置于真空干燥箱中干燥两天，再取上述膦盐放入三口瓶中，加入甲醛水溶液(37％)，剧烈搅拌下缓慢滴加NaOH溶液，控制滴加速率保持体系温度不超过40℃，滴加完全后在常温条件下继续搅拌4h；待反应完成后，用氯仿萃取三口瓶中混合物，将所得萃取液用无水MgSO4干燥2h，过滤得到滤液，通过旋转蒸发器除去溶液中的溶剂得到粗产物，用柱层析法过柱，洗脱剂为乙酸乙酯和石油醚，体积比为1∶49～51，得到淡黄色固体5-乙烯基水杨醛；
(3)N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺的制备：
取2,5-二甲基-1,4苯二胺放入单口圆底烧瓶，用无水乙醇溶解，5-乙烯基水杨醛溶于无水乙醇中，室温下缓慢滴入2,5-二甲基-1,4苯二胺溶液中，2,5-二甲基-1,4苯二胺与5-乙烯基水杨醛的摩尔比为1.0∶2.9～1.0∶3.1滴完后80℃回12h；反应完过滤，固体用无水乙醇和二氯甲烷冲洗多次，得到金黄色粉末N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺；
(4)5-甲酰-8-羟基喹啉的制备：
将8-羟基喹啉以及无水乙醇到三口烧瓶之中，通过搅拌溶解，再慢慢加入氢氧化钠溶液，在回流的条件下缓慢滴加氯仿，8-羟基喹啉与氯仿的摩尔比为1.0∶2.0～1.0∶2.4，继续反应20h以上，待冷却至室温，旋转蒸发仪去除溶剂，倒入蒸馏水中,用10％的稀盐酸酸化至pH为5左右，有砖红色固体析出，抽滤得土黄色固体粗产物并真空干燥，干燥完毕后，将固体研磨成粉，然后用石油醚洗涤8～16h，洗涤所得固体用无水乙醇重结晶，得到橘红色固体5-甲酰-8-羟基喹啉；
(5)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
将摩尔比为1.0∶1.4～1.0∶1.6的5-甲酰基-8-羟基喹啉和氰基乙酸放入三口瓶内，加入乙腈，搅拌使其溶解后加入少量的冰醋酸和哌啶，惰性气体保护下加热至85℃反应8～16h后关闭反应，旋转蒸发至反应混合物近饱和，0℃下冷却6～12h待晶体析出，过滤干燥后粗产物用25％的乙醇重结晶多次，得橘黄色固体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(6)配合物SBD-Cd的制备：
取摩尔比为1.0∶0.9～1.0∶1.1的N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入到单口圆底烧瓶中，室温加入四氢呋喃使其溶解，搅拌下缓慢滴入溶有Cd(CH3COO)2·2H2O的无水甲醇溶液，升温至85℃回流8～16h，反应结束后自然冷却至室温，停止反应，静置2h后过滤，将滤纸上的固体分别用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置72h，得到淡黄色固体产物SBD-Cd；
(7)配合物SBD-Ni、SBD-Cu、SBD-Zn的制备：
配合物SBD-Ni、SBD-Cu、SBD-Zn参照配合物SBD-Cd的具体合成方法，将配位用的Cd(CH3COO)2·2H2O替换为Ni(CH3COO)2·2H2O、Cu(CH3COO)2·2H2O、Zn(CH3COO)2·2H2O，后处理分别得到土黄色固体SBD-Ni、深黄色固体SBD-Cu、橘黄色固体SBD-Zn；
(8)聚合金属配合物BDTT-SBD-Cd的制备：
聚合金属配合物BDTT-SBD-Cd通过Heck聚合反应获得，取摩尔比为1.0∶0.9～1.0∶1.1的配合物单体SBD-Cd和给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT)，再加入催化剂醋酸钯和三(2-甲苯基)膦于反应瓶中，加入精制的DMF和除水的三乙胺，在氮气保护下，90℃反应44～52h；反应停止后加入无水甲醇静置2h，简单过滤，滤渣继续用热的无水甲醇冲洗3～4次，真空干燥72h，得到金黄色固体BDTT-SBD-Cd、；
(9)聚合金属配合物BDTT-SBD-Ni、BDTT-SBD-Cu、BDTT-SBD-Zn的制备：
聚合金属配合物BDTT-SBD-Ni、BDTT-SBD-Cu、BDTT-SBD-Zn的具体合成方法参照BDTT-SBD-Cd的合成，将配合物SBD-Cd替换成SBD-Cd、SBD-Ni、SBD-Cu、SBD-Zn，经过反应处理干燥后分别得到深褐色固体BDTT-SBD-Ni、黄褐色固体BDTT-SBD-Cu、淡黄色固体BDTT-SBD-Zn；
四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的用途：在染料敏化太阳能电池中用作吸收太阳光并产生和传输电子的染料敏化剂材料；
此发明的主要优势在于：(1)发明了四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物，它们是以苯并噻二吩联二噻吩衍生物BDTT为电子给体(D)，以烷基化的水杨醛席夫碱衍生物与金属配位形成的配合物为辅助电子受体(A’)，以2-氰基-3-(8-羟基喹啉-5-基)丙烯酸与金属配位形成π桥、受体(A)和锚定基团，通过Heck反应将给体(D)和配合物受体部分[-A’-(π-A)2]连接而合成的四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni，表现出优良的光伏性能和光电转化效率，制备方法简单，原材料易得；(2)具有良好的热性能和光稳定性，有利于实际应用；
附图说明
图1本发明实施例合成的配体5-氯甲基水杨醛的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图2本发明实施例合成的配体5-乙烯基水杨醛的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图3本发明实施例合成的配体N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图4本发明实施例合成的配体5-甲酰-8-羟基喹啉的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图5本发明实施例合成的配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图6本发明实施例合成的配合物SBD-Cd、SBD-Zn、SBD-Cu、SBD-Ni的红外光谱(FTIR)(KBr，cm-1)；
图7本发明实施例合成的化合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的红外光谱(FTIR)(KBr，cm-1)；
图8本发明实施例合成的化合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的热重分析曲线(TGA)；
图9本发明实施例合成的化合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni作染料敏化剂的染料敏化太阳能电池的电流密度-电压(J-V)曲线；
图10本发明实施例合成的化合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni作染料敏化剂的染料敏化太阳能电池的外量子效率(IPCE)曲线；
具体实施方式
本发明的聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的反应合成路线如下：
下面结合具体实施例对本发明做进一步的说明
实施例1：
四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni，其分子结构式如式3：
上述聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的制备方法：
A.5-氯甲基水杨醛的制备：称取9g(0.3mol)多聚甲醛放入150mL三口圆底烧瓶中，缓慢滴加90mL浓盐酸，充分搅拌后再缓慢滴加15.6mL(0.15mol)水杨醛，在室温条件下搅拌48h，过滤后用饱和碳酸氢钠将上述固体洗至弱碱性，再用蒸馏水反复冲洗至中性，干燥后用石油醚(60-90℃)重结晶，真空干燥后得到白色针状的固体产物，产率为42％，m.p.85～86℃，核磁共振氢谱(1H-NMR)见附图1，1H-NMR(CDCl3,ppm):11.08(s,1H),9.90(s,1H),7.57(s,1H),7.55(d,1H),7.01(d,1H),4.60(s,2H).13C-NMR(CDCl3,ppm):196.22,161.63,137.36,133.66,129.24,120.37,118.34,45.26；
B.5-乙烯基水杨醛的制备：称取6.96g(4mmol)5-氯甲基水杨醛和10.48g(40mmol)三苯基膦于三口烧瓶，加70mL苯溶解，回流反应1h，冷却后过滤，所得固体用少量乙醚分三次洗涤，得白色粉末状固体15.8g，将固体置于真空干燥箱中干燥两天，再称取7.785g(18mmol)上述膦盐放入150mL三口瓶中，加入60mL甲醛水溶液(37％)，剧烈搅拌下缓慢滴加19.5mL 12.5mol·L-1的NaOH溶液，控制滴加速率保持体系温度不超过40℃，滴加完全后在常温条件下继续搅拌4h；待反应完成后，用氯仿萃取三口瓶中混合物，将所得萃取液用无水MgSO4干燥2h，过滤得到滤液，通过旋转蒸发器除去溶液中的溶剂得到粗产物，粗产物通过硅胶柱以乙酸乙酯∶石油醚＝1∶50(v/v)为展开剂过柱，得到淡黄色固体，产率为46％，m.p.19～20℃，核磁共振氢谱(1H-NMR)见附图2，1H-NMR(CDCl3,ppm):11.01(s,1H),9.90(s,1H),7.62(d,1H),7.54(s,1H),6.97(d,1H),6.64-6.71(m,1H),5.67(d,1H),5.24(d,1H).13C-NMR(CDCl3,ppm):191.04,161.04,136.47,136.12,130.84,129.13,127.71,118.43,114.30；
C.N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺的制备：称量取1.36g(10mmol)2,5-二甲基-1,4苯二胺放入100mL单口圆底烧瓶，用20mL无水乙醇溶解，称量3.11g(21mmol)5-乙烯基水杨醛溶于20mL无水乙醇中，室温下缓慢滴入2,5-二甲基-1,4苯二胺溶液中，滴完后80℃回12h；反应完过滤，固体用无水乙醇和二氯甲烷冲洗多次，得到金黄色粉末2.76g，产率75％，m.p.236～237℃；FT-IR(KBr,cm-1):3445cm-1(O-H),3091cm-1(＝CH2),1620cm-1(C＝C),1583cm-1(C＝N).核磁共振氢谱(1H-NMR)见附图3，1H-NMR(CDCl3,ppm):13.25(s,2H),8.69(s,2H),7.49-7.52(d,2H),7.45(s,2H),7.39(s,4H),7.02-7.04(d,2H),6.66-6.73m,2H),5.64-5.69(d,2H),5.19-5.21(d,2H).13C-NMR(CDCl3,ppm):162.25,161.10,147.13,135.58,130.96,130.20,129.18,122.31,118.94,117.57,112.04；
D.5-甲酰-8-羟基喹啉的制备：将25g(172mmol)的8-羟基喹啉以及100ml无水乙醇加入250ml三口烧瓶之中，通过搅拌溶解，再慢慢加入氢氧化钠溶液(氢氧化钠50g溶于蒸馏水50ml中)，在回流的条件下缓慢滴加45g(383mmol)氯仿，继续反应20h，待冷却至室温，旋转蒸发去除溶剂，倒入600ml蒸馏水中,用浓盐酸与蒸馏水体积比1.0∶4.0的稀盐酸酸化至pH为5左右，有砖红色固体析出，抽滤得土黄色固体粗产物并真空干燥，干燥完毕后，将固体研磨成粉，然后用石油醚抽提12h，抽提所得固体用无水乙醇重结晶，得到橘红色固体4.3g，产率14.4％；m.p.172.2-173.5℃；核磁共振氢谱(1H-NMR)(CDCl3,ppm)见附图4,1H-NMR(CDCl3,ppm):10.14(s,1H),9.68-9.69(d,1H),8.89-8.96(d,1H),7.98-8.02(d,1H),7.65-7.68(q,1H),7.29-7.31(d,1H).13C-NMR(CDCl3,ppm):192.07，157.84，148.74，140.48，137.85，134.77，126.59，124.74，123.56，108.99；
E.2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：向250mL三口烧瓶中加入1.04g(6mmol)5-甲酰基-8羟基喹啉和0.77g(9mmol)氰基乙酸，用20mL乙腈溶解，随后加入3mL冰醋酸，并滴加5滴哌啶，升温至85℃，反应24h，停止加热，旋转蒸发除去部分溶液，在0℃条件下过夜；过滤，所得固体用氯仿冲洗数次，真空干燥，再用25％乙醇重结晶，得到金黄色的固体产物0.68g，产率58％，m.p.200～201℃,FTIR(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)；核磁共振氢谱(1H-NMR)见附图5,1H-NMR(DMSO-d6,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).13C-NMR(CDCl3,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；
F.配合物SBD-Cd的制备：分别称取0.198g(0.5mmol)2,2-(2,5-二甲基-1,4-亚苯基)双(4-乙烯基苯酚)和0.264g(1.1mmol)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入到100mL的单口圆底烧瓶中，室温加入15mL四氢呋喃使其溶解，搅拌下缓慢滴入20mL溶有0.280g(1.05mmol)Cd(CH3COO)2·2H2O的无水甲醇溶液，升温至85℃回流12h，反应结束后自然冷却至室温，停止反应，静置2h后过滤，将滤纸上的固体分别用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置72h，经处理后得到淡黄色固体产物0.346g，产率为63％；红外谱图(FT-IR)(KBr,cm-1)见附图6,FT-IR(KBr,cm-1):3445cm-1(O-H),2925cm-1(-CH3),2211cm-1(C≡N),1601cm-1(C＝C),1558cm-1(C＝N),1100cm-1(C-O-Cd),496cm-1(N-Cd).Anal.Calcd.for[C52H36Cd2N6O8]:C,56.90；H,3.31；N,7.66％.Found:C,56.98；H,3.35；N,7.59％；
G.配合物SBD-Ni的制备：配合物SBD-Ni参照镉配合物SBD-Cd的合成方法，将Cd(CH3COO)2·2H2O替换为0.261g(1.05mmol)的乙酸镍(Ni(CH3COO)2·4H2O)，处理后得到土黄色固体产物0.331g，产率67％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3424cm-1(O-H),2924cm-1(-CH3),2207cm-1(C≡N),1598cm-1(C＝C),1559cm-1(C＝N),1107cm-1(C-O-Cd),494cm-1(N-Cd).Anal.Calcd.for[C52H36Ni2N6O8]:C,63.07；H,3.66；N,8.49％.Found:C,63.96；H,3.40；N,8.44％；
H.配合物SBD-Cu的制备：配合物SBD-Cu参照配合物SBD-Cd的具体合成方法，将Cd(CH3COO)2·2H2O替换为0.210g(1.05mmol)醋酸铜Cu(CH3COO)2·H2O，经处理后得到深黄色固体产物0.23g，产率为46％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3419cm-1(O-H),2925cm-1(-CH3),2210cm-1(C≡N),1607cm-1(C＝C),1565cm-1(C＝N),1112cm-1(C-O-Cd),513cm-1(N-Cd).Anal.Calcd.for[C52H36Cu2N6O8]:C,62.46；H,3.63；N,8.40％.Found:C,63.21；H,3.78；N,8.25％；
I.配合物SBD-Zn的制备：配合物SBD-Zn参照配合物SBD-Cd的具体合成方法，将Cd(CH3COO)2·2H2O替换为0.231g(1.05mmol)Zn(CH3COO)2·2H2O，经处理后得到橘黄色固体0.261g，产率为52％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3427cm-1(O-H),2923cm-1(-CH3),2211cm-1(C≡N),1605cm-1(C＝C),1562cm-1(C＝N),1112cm-1(C-O-Cd),502cm-1(N-Cd).Anal.Calcd.for[C52H36Zn2N6O8]:C,62.23；H,3.62；N,8.37％.Found:C,63.04；H,3.56；N,8.14％；
J.聚合金属配合物BDTT-SBD-Cd的制备：聚合金属配合物BDTT-SP-Cd通过Heck聚合反应获得，依次称取配合物单体SBD-Cd(0.329g,0.3mmol)，给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT)(0.236g,0.32mmol)，催化剂醋酸钯(Pd(CH3COO)2,0.0029g,0.013mmol)和三(2-甲苯基)膦(0.022g,0.072mmol)于反应瓶中，加入12mL精制的DMF和除水的三乙胺(3mL)，在氮气保护下，90℃反应48h；反应停止后加入20mL无水甲醇静置2h，简单过滤，滤渣继续用热的无水甲醇冲洗3～4次，真空干燥72h，得到金黄色固体0.227g，产率为44％；红外谱图(FT-IR)(KBr,cm-1)见附图7，FT-IR(KBr,cm-1):3445cm-1(O-H),2925cm-1,2857cm-1(C-H),2208cm-1(C≡N),1600cm-1(C＝C),1558cm-1(C＝N),1092cm-1(C-O-Cd),494cm-1(N-Cd)；
K.聚合金属配合物BDTT-SBD-Ni的制备：聚合金属配合物BDTT-SBD-Ni的具体合成方法参照BBDTT-SBD-Cd的合成，称取的0.329g配合物SBD-Cd换为0.297g配合物SBD-Ni(0.3mmol)，经过反应处理后真空干燥得到深褐色固体产物0.198g，产率41％，红外谱图(FT-IR)(KBr,cm-1)见附图7，FT-IR(KBr,cm-1):3367cm-1(O-H),2924cm-1,2857cm-1(C-H),2207cm-1(C≡N),1596cm-1(C＝C),1556cm-1(C＝N),1105cm-1(C-O-Ni),493cm-1(N-Ni)；
L.聚合金属配合物BDTT-SBD-Cu的制备：聚合金属配合物BDTT-SBD-Cu的具体合成方法参照BDTT-SBD-Cd的合成，称取的0.329g配合物SBD-Cd换为0.300g配合物SBD-Ni(0.3mmol)，经过反应处理干燥后得到黄褐色固体0.229g，产率为47％；红外谱图(FT-IR)(KBr,cm-1)见附图7，FT-IR(KBr,cm-1):3413cm-1(O-H),2926cm-1,2858cm-1(C-H),2209cm-1(C≡N),1596cm-1(C＝C),1562cm-1(C＝N),1111cm-1(C-O-Cu),510cm-1(N-Cu)；
M.聚合金属配合物BDTT-SBD-Zn的制备：聚合金属配合物BDTT-SBD-Zn的具体合成方法参照BDTT-SBD-Cd的合成，称取的0.329g配合物SBD-Cd换为0.296g配合物SBD-Zn(0.3mmol)，经过反应处理干燥后得到淡黄色固体0.252g，产率52％，红外谱图(FT-IR)(KBr,cm-1)见附图7，FT-IR(KBr,cm-1):3418cm-1(O-H),2925cm-1,2857cm-1(C-H),2210cm-1(C≡N),1603cm-1(C＝C),1560cm-1(C＝N),1112cm-1(C-O-Zn),492cm-1(N-Zn)。
实施例2：
测定聚合烷基化水杨醛席夫碱衍生物合金属配合物染料敏化BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的热重分析(TGA)曲线，方法：SDTQ600的热重分析仪，N2保护下以20℃/min的升温速度进行测试，测试结果如图8。
实施例3：
测定聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的分子量，方法为凝胶渗透色谱(GPC)：使用Waters-1515型号的凝胶渗透色谱仪，分离柱为waters styragel columns(103，104，
)，柱温箱温度80℃，以DMF为流动相，聚苯乙烯溶液作参比，流速为1.00mL/min进行测试，测试结果如表1。
表1基于聚合烷基化水杨醛席夫碱衍生物合金属配合物的DSSCs的分子量测试数据
实施例4：
J-V曲线测试光源为氙灯模拟的光强100mW/cm2的AM 1.5G的太阳光，通过Keithley 2400数字源表改变电压并记录电流随电压的变化值；IPCE测试由OrielCornerstone单色仪提供光源，在短路条件下测得，波长的测试间隔为10nm，DSSC的有效工作面积为0.25cm2；测定以聚合烷基化水杨醛席夫碱衍生物合金属配合物染料敏化剂BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni为染料敏化剂的染料敏化太阳能电池的性能参数和光电转换效率，其电池电流密度-电压(J-V)曲线如图9，电池外量子效率(IPCE)曲线如图10；表2是它们的光伏性能和光电转换效率测试结果。
表2基于聚合烷基化水杨醛席夫碱衍生物金属配合物的DSSC的光伏性能数据
Claims (2)
1.四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni，其结构式如下：
如上所述的四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的制备方法：
(1)5-氯甲基水杨醛的制备：
称取多聚甲醛至三口瓶中，沿壁迟缓加入大量的浓盐酸，待搅拌均匀后，缓慢滴加水杨醛，多聚甲醛和水杨醛的摩尔比为1.8∶1.0～2.2∶1.0，室温搅拌反应36～72h，过滤得到粗产物白色固体，依次用饱和碳酸氢钠溶液和蒸馏水洗涤至中性后放置干燥箱干燥，粗产物用石油醚重结晶多次，得到白色针状固体5-氯甲基水杨醛；
(2)5-乙烯基水杨醛的制备：
取摩尔比为1∶9～11的5-氯甲基水杨醛和三苯基膦于三口烧瓶，加苯溶解，回流反应1h，冷却后过滤，所得固体用少量乙醚分三次洗涤，得白色粉末状固体，将固体置于真空干燥箱中干燥两天，再取上述膦盐放入三口瓶中，加入浓度为37％甲醛水溶液，剧烈搅拌下缓慢滴加NaOH溶液，控制滴加速率保持体系温度不超过40°C，滴加完全后在常温条件下继续搅拌4h；待反应完成后，用氯仿萃取三口瓶中混合物，将所得萃取液用无水MgSO4干燥2h，过滤得到滤液，通过旋转蒸发器除去溶液中的溶剂得到粗产物，用柱层析法过柱，洗脱剂为乙酸乙酯和石油醚，体积比为1∶49～51，得到淡黄色固体5-乙烯基水杨醛；
(3)N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺的制备：
取2,5-二甲基-1,4苯二胺放入单口圆底烧瓶，用无水乙醇溶解，5-乙烯基水杨醛溶于无水乙醇中，室温下缓慢滴入2,5-二甲基-1,4苯二胺溶液中，2,5-二甲基-1,4苯二胺与5-乙烯基水杨醛的摩尔比为1.0∶2.9～1.0∶3.1滴完后80℃回12h；反应完过滤，固体用无水乙醇和二氯甲烷冲洗多次，得到金黄色粉末N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺；
(4)5-甲酰-8-羟基喹啉的制备：
将8-羟基喹啉以及无水乙醇到三口烧瓶之中，通过搅拌溶解，再慢慢加入氢氧化钠溶液，在回流的条件下缓慢滴加氯仿，8-羟基喹啉与氯仿的摩尔比为1.0∶2.0～1.0∶2.4，继续反应20h以上，待冷却至室温，旋转蒸发仪去除溶剂，倒入蒸馏水中,用10％的稀盐酸酸化至pH为5，有砖红色固体析出，抽滤得土黄色固体粗产物并真空干燥，干燥完毕后，将固体研磨成粉，然后用石油醚洗涤8～16h，
洗涤所得固体用无水乙醇重结晶，得到橘红色固体5-甲酰-8-羟基喹啉；
(5)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
将摩尔比为1.0∶1.4～1.0∶1.6的5-甲酰基-8-羟基喹啉和氰基乙酸放入三口瓶内，加入乙腈，搅拌使其溶解后加入少量的冰醋酸和哌啶，惰性气体保护下加热至85°C反应8～16h后关闭反应，旋转蒸发至反应混合物近饱和，0°C下冷却6～12h待晶体析出，过滤干燥后粗产物用25％的乙醇重结晶多次，得橘黄色固体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(6)配合物SBD-Cd的制备：
取摩尔比为1.0∶0.9～1.0∶1.1的N,N-双((5-乙烯基吡啶-2-基)亚甲基)苯-1,4-二胺和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入到单口圆底烧瓶中，室温加入四氢呋喃使其溶解，搅拌下缓慢滴入溶有Cd(CH3COO)2·2H2O的无水甲醇溶液，升温至85℃回流8～16h，反应结束后自然冷却至室温，停止反应，静置2h后过滤，将滤纸上的固体分别用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置72h，得到淡黄色固体产物SBD-Cd；
(7)配合物SBD-Ni、SBD-Cu、SBD-Zn的制备：
配合物SBD-Ni、SBD-Cu、SBD-Zn参照配合物SBD-Cd的具体合成方法，将配位用的Cd(CH3COO)2·2H2O替换为Ni(CH3COO)2·2H2O、Cu(CH3COO)2·2H2O、Zn(CH3COO)2·2H2O，后处理分别得到土黄色固体SBD-Ni、深黄色固体SBD-Cu、橘黄色固体SBD-Zn；
(8)聚合金属配合物BDTT-SBD-Cd的制备：
聚合金属配合物BDTT-SBD-Cd通过Heck聚合反应获得，取摩尔比为1.0∶0.9～1.0∶1.1的配合物单体SBD-Cd和给体单体2,6-二溴-4,8-二(5-(2-乙基辛基)噻吩-2-基)苯并[1,2-b:4,5-b']二噻吩(BDTT)，再加入催化剂醋酸钯和三(2-甲苯基)膦于反应瓶中，加入精制的DMF和除水的三乙胺，在氮气保护下，90℃反应44～52h；反应停止后加入无水甲醇静置2h，简单过滤，滤渣继续用热的无水甲醇冲洗3～4次，真空干燥72h，得到金黄色固体BDTT-SBD-Cd、；
(9)聚合金属配合物BDTT-SBD-Ni、BDTT-SBD-Cu、BDTT-SBD-Zn的制备：
聚合金属配合物BDTT-SBD-Ni、BDTT-SBD-Cu、BDTT-SBD-Zn的具体合成方法参照BDTT-SBD-Cd的合成，将配合物SBD-Cd替换成SBD-Cd、SBD-Ni、SBD-Cu、SBD-Zn，经过反应处理干燥后分别得到深褐色固体BDTT-SBD-Ni、黄褐色固体BDTT-SBD-Cu、淡黄色固体BDTT-SBD-Zn。
2.根据权利要求1所述的四种D-A’-(π-A)2型聚合烷基化水杨醛席夫碱衍生物合金属配合物BDTT-SBD-Cd、BDTT-SBD-Zn、BDTT-SBD-Cu、BDTT-SBD-Ni的用途，在染料敏化太阳能电池中用作染料敏化剂。
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