CN112225883B - 四种D-A’-(π-A)2型聚合吡啶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型聚合吡啶衍生物合金属配合物及其制备方法与用途 Download PDFInfo
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Abstract
本发明涉及式1所示的四种D‑A’‑(π‑A)2型聚合吡啶衍生物合金属配合物BDTT‑PP‑Cd、BDTT‑PP‑Zn、BDTT‑PP‑Cu、BDTT‑PP‑Ni及其制备方法与用途，它们以功能化的吡啶衍生物作为主配体与金属配位形成的金属配合物为辅助电子配体A’，以苯并二噻吩联二噻吩(BDTT)为电子给体D，通过Heck反应合成D‑A’‑(π‑A)2型的吡啶衍生物合金属配合物，实验基于以BDTT‑PP‑Cd、BDTT‑PP‑Zn、BDTT‑PP‑Cu、BDTT‑PP‑Ni为染料敏化剂的染料敏化太阳能电池的光伏性能测试表现出较好的效果：光电转化效率(PCE)分别达到8.94％、8.09％、6.87％、6.34％，其热分解温度均达到了232℃以上，热稳定性良好，这将在染料敏化太阳能电池的开发应用方面具有一定的前景。
Description
技术领域
本发明涉及四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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
自染料敏化太阳能电池(DSSCs)问世以来，其主要组成部分如电极材料、染料敏化剂等都在不断地改进，染料敏化剂是电池中最关键的组成部分，从最开始的D-A结构通过不断探索发展到了当今主流D-A'-π-A型结构的光敏剂，该类型结构的染料分子最大的优势在于能通过改变辅助受体A'及其吸电子能力来调节染料分子间的推拉电子平衡和调整分子的HOMO与LUMO能级，达到拓宽光敏剂在可见光区和近红外区的吸收光谱，并使最大吸收峰红移的目的。因而对D-A'-π-A型敏化剂的设计、合成与应用研究成为了该领域的重点和热点。本发明研究以吸电子能力强，且通过调节配位键强度而能调节吸电子能力大小的吡啶衍生物合金属配合物做辅助电子受体A’，并将给体(D)连接两个受体部分[-A’-(π-A)2]以增加受体部分的吸拉电子能力，而制备了四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni，测试应用表明它们具有较好的吸光性能与光伏性能。
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)，以功能化的吡啶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型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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8.94％、8.09％、6.87％、6.34％，其结构通式如下：
四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni的制备方法：
(1)5-乙烯基吡啶-2-甲醛的制备：
取摩尔比为1.0∶1.0～1.0∶1.2的5-溴吡啶二甲醛、乙烯基三氟硼酸钾，再将三苯基膦二氯化钯和碳酸铯加入圆底烧瓶中，加入四氢呋喃和少量水做溶剂，在氮气保护下回流18～30h冷却至室温，真空旋干部分溶剂，先后加入适量去离子水和二氯甲烷使反应瓶中的固体全部溶解，再用二氯甲烷萃取三次，取有机层旋干，所得粗产物用柱层析法过柱，洗脱剂为二氯甲烷和石油醚，其体积比为1.0∶0.9～1.1，得到无色透明液体5-乙烯基吡啶-2-甲醛；
(2)N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺的制备：
取对苯二胺放入单口圆底烧瓶，用无水乙醇溶解，加入少量无水硫酸镁；取5-乙烯基吡啶-2-甲醛溶于无水乙醇中，室温下缓慢滴入对苯二胺溶液中，对苯二胺与5-乙烯基吡啶-2-甲醛的摩尔比为1.0∶2.0～1.0∶2.2，滴加完后85℃回流8～16h；反应完趁热过滤，滤液真空旋干，用无水乙醇重结晶，得到黄色的晶状固体产物N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺；
(3)5-甲酰基-8-羟基喹啉的制备：
向三口烧瓶中加入8-羟基喹啉和无水乙醇，搅拌下加入NaOH溶液，回流反应后向反应体系中缓慢滴加氯仿，8-羟基喹啉与氯仿的摩尔比为1.0∶2.0～1.0∶2.4，滴毕，继续回流18～22h，停止反应后，低温旋干多余的氯仿和乙醇，将剩余固体倒入烧杯并加入蒸馏水至最大刻度，搅拌下缓慢滴加稀盐酸至出现大量砖红色絮状固体，抽滤，得到黄色固体，将所得粗产物放至烘箱中干燥完全，研磨，用石油醚洗涤20～28h，再用乙醇重结晶，真空干燥24～48h，得到粉红色固体5-甲酰基-8-羟基喹啉；
(4)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
向三口烧瓶中加入5-甲酰基-8羟基喹啉和氰基乙酸，5-甲酰基-8-羟基喹啉和氰基乙酸的摩尔比为1.0∶1.4～1.0∶1.6，再用乙腈溶解，随后加冰醋酸并滴加少量的哌啶，升温至85℃，反应20～28h，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，得到金黄色固体产物2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(5)配合物PP-Cd的制备：
取摩尔比为1.0∶2.0～1.0∶2.2的N1,N4-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入到圆底烧瓶中，室温加入四氢呋喃使其溶解，搅拌下缓慢滴入Cd(CH3COO)2·2H2O的无水甲醇溶液，升温至85℃回流8～16h，停止反应，静置2h后过滤，将滤纸上的固体分别热的用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置64～80h，得到土黄色固体PP-Cd；
(6)配合物PP-Ni、PP-Cu、PP-Zn的制备：
配合物PP-Ni、PP-Cu、PP-Zn参照配合物PP-Cd的具体合成方法，将配位用的Cd(CH3COO)2·2H2O分别替换为Zn(CH3COO)2·2H2O、Cu(CH3COO)2·2H2O、Ni(CH3COO)2·2H2O，经处理后分别得到土黄色固体产物PP-Ni、黄褐色固体PP-Cu、橘黄色固体PP-Zn；
(7)聚合金属配合物BDTT-PP-Cd的制备：
聚合金属配合物BDTT-PP-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PP-Cd和给体单体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42～54h，反应停止后加入无水甲醇静置2h，过滤后，滤渣继续用热的无水甲醇冲洗3～4次，真空干燥64～80h，得到红褐色固体聚合金属配合物BDTT-PP-Cd；
(8)聚合金属配合物BDTT-PP-Ni、BDTT-PP-Cu、BDTT-PP-Zn的制备：
聚合金属配合物BDTT-PP-Ni、BDTT-PP-Cu、BDTT-PP-Zn的具体合成方法参照BDTT-PP-Cd的合成，将PP-Cd分别替换成PP-Ni、PP-Cu、PP-Zn，经过反应处理干燥后分别得到黑色固体产物BDTT-PP-Ni、黑色固体产物BDTT-PP-Cu、红褐色固体产物BDTT-PP-Zn；
四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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型聚合吡啶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)，以功能化的吡啶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型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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-乙烯基吡啶-2-甲醛的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图2本发明实施例合成的配体N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图3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4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5本发明实施例合成的配合物PP-Cd、PP-Zn、PP-Cu、PP-Ni的红外光谱(FTIR)(KBr，cm-1)；
图6本发明实施例合成的化合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni的热重分析曲线(TGA)；
图8本发明实施例合成的化合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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9本发明实施例合成的化合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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
本发明的聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni，其分子结构式如下：
上述聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni的制备方法：
A.5-乙烯基吡啶-2-甲醛的制备：分别称取1.68g(10mmol)5-溴吡啶二甲醛、1.45g(11mmol)乙烯基三氟硼酸钾、0.007g(0.1mmol)三苯基膦二氯化钯和9.77g(30mmol)碳酸铯加入100mL圆底烧瓶中，加入18mL四氢呋喃和2mL水做溶剂，在氮气保护下回流22h，冷却至室温，真空旋干部分溶剂，先后加入适量去离子水和二氯甲烷使反应瓶中的固体全部溶解，再用二氯甲烷萃取三次，取有机层旋干，所得粗产物用二氯甲烷∶石油醚＝1∶1(v/v)，得到无色透明的液体产物0.72g，产率52.6％，m.p.7～8℃，核磁共振氢谱(1H-NMR)见附图1，1H-NMR(CDCl3,ppm):10.10(s,1H),8.81(s,1H),7.97-7.99(d,1H),7.92-7.94(d,1H),6.79-6.86(m,1H),6.02-6.06(d,1H),5.59-5.62(d,1H)；
B.N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺的合成的制备：取1.08g(10mmol)对苯二胺放入100mL单口圆底烧瓶，用20mL无水乙醇溶解，加入少量无水硫酸镁；称量2.79g(21mmol)5-乙烯基吡啶-2-甲醛溶于20mL无水乙醇中，室温下缓慢滴入对苯二胺溶液中，滴加完后85℃回流12h；反应完趁热过滤，滤液真空旋干，用无水乙醇重结晶，得到黄色的晶状固体产物2.31g，产率为68％，m.p,161～162℃,核磁共振氢谱(1H-NMR)见附图2,FTIR(KBr,cm-1):3084cm-1(＝C-H),1614cm-1(C＝C),1577cm-1(C＝N).1H-NMR(CDCl3,ppm):8.76(s,2H),8.70(s,2H),8.22-8.24(d,2H),7.91-7.93(d,2H),7.43(s,4H),6.79-6.86(m,2H),5.98-6.02(d,2H),5.52-5.55(d,2H)；13C-NMR(CDCl3,ppm):159.76,153.78,149.60,148.27,134.49,133.23,133.09,122.28,121.81,117.66；
C.5-甲酰基-8-羟基喹啉的制备：向500mL三口烧瓶中加入25g(172mmol)8-羟基喹啉和100mL无水乙醇，搅拌下加入NaOH溶液(NaOH 50g，H2O 65mL)，回流反应后向反应体系中缓慢滴加45g(380mmol)CHCl3，滴毕，继续回流20h，停止反应后，低温旋干多余的氯仿和乙醇，将剩余固体倒入1000mL烧杯并加入蒸馏水至最大刻度，搅拌下缓慢滴加稀盐酸至出现大量砖红色絮状固体；抽滤，得到黄色固体，将所得粗产物放至烘箱中干燥完全，研磨，用石油醚洗涤24h，再用乙醇重结晶，真空干燥36h，得到粉红色的固体3.65g，产率12％，m.p.172～173℃，FTIR(KBr,cm-1):3447cm-1(-OH),2920cm-1(C-H),1690cm-1(C＝O),1576cm-1(C＝C),1510cm-1(C＝N).核磁共振氢谱(1H-NMR)见附图3,1H-NMR(CDCl3,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).13C-NMR(CDCl3,ppm):192.04,157.86,148.74,140.45,137.85,134.76,126.59,124.72,123.56,109.02；
D.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4,1H-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；
E.亚胺衍生物合镉配合物(PP-Cd)的制备：分别称取0.169g(0.5mmol)N1,N4-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺和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，停止反应，静置2h后过滤，将滤纸上的固体分别热的用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置72h，得到土黄色的固体产物0.297g，产率为51％，红外谱图(FT-IR)见附图5，FT-IR(KBr,cm-1):3437cm-1(O-H),2206cm-1(C≡N),1594cm-1(C＝C),1560cm-1(C＝N),1109cm-1(C-O-Cd),505cm-1(N-Cd).Anal.Calcd.for[C52H38Cd2N8 O10]:C,53.85；H,3.30；N,9.66％.Found:C,54.12；H,3.45；N,9.58％；
F.亚胺衍生物合镍配合物(PP-Ni)的制备：镍配合物(PP-Ni)参照镉配合物(PP-Cd)的具体合成方法，将配位用的Cd(CH3COO)2·2H2O替换为0.261g(1.05mmol)的乙酸镍(Ni(CH3COO)2·4H2O)，经处理后得到土黄色固体产物0.322g，产率为61％，红外谱图(FT-IR)见附图5，FT-IR(KBr,cm-1):3413cm-1(O-H),2207cm-1(C≡N),1598cm-1(C＝C),1562cm-1(C＝N),1108cm-1(C-O-Cd),499cm-1(N-Cd).Anal.Calcd.for[C52H38Ni2N8O10]:C,59.35；H,3.64；N,10.65％.Found:C,59.98；H,4.02；N,10.13％；
G.亚胺衍生物合铜配合物(PP-Cu)的制备：铜配合物(PP-Cu)参照镉配合物(PP-Cd)的具体合成方法，将配位用的Cd(CH3COO)2·2H2O替换为0.210g(1.05mmol)Cu(CH3COO)2·H2O，经处理后得到黄褐色固体0.302g，产率为57％，红外谱图(FT-IR)见附图5,FT-IR(KBr,cm-1):3438cm-1(O-H),2210cm-1(C≡N),1595cm-1(C＝C),1556cm-1(C＝N),1117cm-1(C-O-Cd),510cm-1(N-Cd).Anal.Calcd.for[C52H38Cu2N8O10]:C,58.81；H,3.61；N,10.55％.Found:C,59.04；H,3.96；N,10.51％；
H.亚胺衍生物合锌配合物(PP-Zn)的制备：锌配合物(PP-Zn)参照镉配合物(PP-Cd)的具体合成方法，将配位用的Cd(CH3COO)2·2H2O替换为0.231g(1.05mmol)Zn(CH3COO)2·2H2O，经处理后得到橘黄色的固体产物0.303g，产率为57％，红外谱图(FT-IR)见附图5,FT-IR(KBr,cm-1):3425cm-1(O-H),2207cm-1(C≡N),1596cm-1(C＝C),1561cm-1(C＝N),1112cm-1(C-O-Cd),507cm-1(N-Cd).Anal.Calcd.for[C52H38Zn2N8O10]:C,58.61；H,3.59；N,10.51％.Found:C,58.65；H,4.05；N,10.03％；
I.聚合金属配合物BDTT-PP-Cd的制备：聚合镉金属配合物BDTT-PP-Cd通过Heck聚合反应获得，依次称取配合物单体PP-Cd(0.347g,0.3mmol)，给体单体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7mL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，得到红褐色固体0.215g，产率38％，红外谱图(FT-IR)见附图6，FT-IR(KBr,cm-1):3365cm-1(O-H),2927cm-1,2858cm-1(C-H),2205cm-1(C≡N),1593cm-1(C＝C),1559cm-1(C＝N),1108cm-1(C-O-Cd),501cm-1(N-Cd)；
J.聚合金属配合物BDTT-PP-Ni的制备：聚合镍金属配合物BDTT-PP-Ni的具体合成方法参照BDTT-PP-Cd的合成，称取的0.347g镉配合物PP-Cd换为0.315g镍配合物PP-Ni(0.3mmol)，经过反应处理干燥后得到黑色固体产物0.256g，产率51％，红外谱图(FT-IR)见附图6，FT-IR(KBr,cm-1):3369cm-1(O-H),2922cm-1,2856cm-1(C-H),2203cm-1(C≡N),1595cm-1(C＝C),1560cm-1(C＝N),1104cm-1(C-O-Ni),495cm-1(N-Ni)；
K.聚合金属配合物BDTT-PP-Cu的制备：聚合铜金属配合物BDTT-PP-Cu的具体合成方法参照BDTT-PP-Cd的合成，称取的0.347g镉配合物PP-Cd换为0.318g铜配合物PP-Cu(0.3mmol)，经过反应处理干燥后得到黑色固体产物0.227g，产率45％，红外谱图(FT-IR)见附图6，FT-IR(KBr,cm-1):3413cm-1(O-H),2925cm-1,2852cm-1(C-H),2206cm-1(C≡N),1593cm-1(C＝C),1554cm-1(C＝N),1113cm-1(C-O-Cu),502cm-1(N-Cu)；
L.聚合金属配合物BDTT-PP-Zn的制备：聚合锌金属配合物BDTT-PP-Zn的具体合成方法参照BDTT-PP-Cd的合成，称取的0.347g镉配合物PP-Cd换为0.319g锌配合物PP-Zn(0.3mmol)，经过反应处理，真空干燥后得到红褐色固体产物0.217g，产为率43％，红外谱图(FT-IR)见附图6，FT-IR(KBr,cm-1):3380cm-1(-H),2923cm-1,2853cm-1(C-H),2206cm-1(C≡N),1596cm-1(C＝C),1561cm-1(C＝N),1112cm-1(C-O-Zn),506cm-1(N-Zn)。
实施例2：
测定聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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7。
实施例3：
测定聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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基于聚合吡啶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；测定以聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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8，电池外量子效率(IPCE)曲线如图9；表2是它们的光伏性能和光电转换效率测试结果。
表2基于聚合吡啶衍生物合金属配合物的DSSCs的光伏性能数据
Claims (2)
1.四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni，其结构式如下：
如上所述的四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-Ni的制备方法：
(1)5-乙烯基吡啶-2-甲醛的制备：
取摩尔比为1.0∶1.0～1.0∶1.2的5-溴吡啶二甲醛、乙烯基三氟硼酸钾，再将三苯基膦二氯化钯和碳酸铯加入圆底烧瓶中，加入四氢呋喃和少量水做溶剂，在氮气保护下回流18～30h冷却至室温，真空旋干部分溶剂，先后加入适量去离子水和二氯甲烷使反应瓶中的固体全部溶解，再用二氯甲烷萃取三次，取有机层旋干，所得粗产物用柱层析法过柱，洗脱剂为二氯甲烷和石油醚，其体积比为1.0∶0.9～1.1，得到无色透明液体5-乙烯基吡啶-2-甲醛；
(2)N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺的制备：
取对苯二胺放入单口圆底烧瓶，用无水乙醇溶解，加入少量无水硫酸镁；取5-乙烯基吡啶-2-甲醛溶于无水乙醇中，室温下缓慢滴入对苯二胺溶液中，对苯二胺与5-乙烯基吡啶-2-甲醛的摩尔比为1.0∶2.0～1.0∶2.2，滴加完后85℃回流8～16h；反应完趁热过滤，滤液真空旋干，用无水乙醇重结晶，得到黄色的晶状固体产物N,N-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺；
(3)5-甲酰基-8-羟基喹啉的制备：
向三口烧瓶中加入8-羟基喹啉和无水乙醇，搅拌下加入NaOH溶液，回流反应后向反应体系中缓慢滴加氯仿，8-羟基喹啉与氯仿的摩尔比为1.0∶2.0～1.0∶2.4，滴毕，继续回流18～22h，停止反应后，低温旋干多余的氯仿和乙醇，将剩余固体倒入烧杯并加入蒸馏水至最大刻度，搅拌下缓慢滴加稀盐酸至出现大量砖红色絮状固体，抽滤，得到黄色固体，将所得粗产物放至烘箱中干燥完全，研磨，用石油醚洗涤20～28h，再用乙醇重结晶，真空干燥24～48h，得到粉红色固体5-甲酰基-8-羟基喹啉；
(4)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
向三口烧瓶中加入5-甲酰基-8羟基喹啉和氰基乙酸，5-甲酰基-8-羟基喹啉和氰基乙酸的摩尔比为1.0∶1.4～1.0∶1.6，再用乙腈溶解，随后加冰醋酸并滴加少量的哌啶，升温至85℃，反应20～28h，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，得到金黄色固体产物2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(5)配合物PP-Cd的制备：
取摩尔比为1.0∶2.0～1.0∶2.2的N1,N4-双(5-乙烯基吡啶-2-亚甲基)苯-1,4-二胺和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入到圆底烧瓶中，室温加入四氢呋喃使其溶解，搅拌下缓慢滴入Cd(CH3COO)2·2H2O的无水甲醇溶液，升温至85℃回流8～16h，停止反应，静置2h后过滤，将滤纸上的固体分别热的用四氢呋喃和无水甲醇冲洗多次，真空干燥箱中放置64～80h，得到土黄色固体PP-Cd；
(6)配合物PP-Ni、PP-Cu、PP-Zn的制备：
配合物PP-Ni、PP-Cu、PP-Zn参照配合物PP-Cd的具体合成方法，将配位用的Cd(CH3COO)2·2H2O分别替换为Zn(CH3COO)2·2H2O、Cu(CH3COO)2·2H2O、Ni(CH3COO)2·2H2O，经处理后分别得到土黄色固体产物PP-Ni、黄褐色固体PP-Cu、橘黄色固体PP-Zn；
(7)聚合金属配合物BDTT-PP-Cd的制备：
聚合金属配合物BDTT-PP-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PP-Cd和给体单体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42～54h，反应停止后加入无水甲醇静置2h，过滤后，滤渣继续用热的无水甲醇冲洗3～4次，真空干燥64～80h，得到红褐色固体聚合金属配合物BDTT-PP-Cd；
(8)聚合金属配合物BDTT-PP-Ni、BDTT-PP-Cu、BDTT-PP-Zn的制备：
聚合金属配合物BDTT-PP-Ni、BDTT-PP-Cu、BDTT-PP-Zn的具体合成方法参照BDTT-PP-Cd的合成，将PP-Cd分别替换成PP-Ni、PP-Cu、PP-Zn，经过反应处理干燥后分别得到黑色固体产物BDTT-PP-Ni、黑色固体产物BDTT-PP-Cu、红褐色固体产物BDTT-PP-Zn。
2.根据权利要求1所述的四种D-A’-(π-A)2型聚合吡啶衍生物合金属配合物BDTT-PP-Cd、BDTT-PP-Zn、BDTT-PP-Cu、BDTT-PP-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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