CN113321789B - 四种含吡咯衍生物的聚合金属配合物染料敏化剂及其制备方法与用途 - Google Patents
四种含吡咯衍生物的聚合金属配合物染料敏化剂及其制备方法与用途 Download PDFInfo
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- CN113321789B CN113321789B CN202010703859.4A CN202010703859A CN113321789B CN 113321789 B CN113321789 B CN 113321789B CN 202010703859 A CN202010703859 A CN 202010703859A CN 113321789 B CN113321789 B CN 113321789B
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Abstract
本发明涉及式1所示的四种D‑A’‑π‑A型含吡咯衍生物的聚合金属配合物BDTT‑py‑Cd、BDTT‑py‑Zn、BDTT‑py‑Cu和BDTT‑py‑Ni及其制备方法与用途，它们是以N‑吡啶基‑2‑乙烯基吡咯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型聚合金属配合物，实验基于以BDTT‑py‑Cd、BDTT‑py‑Zn、BDTT‑py‑Cu和BDTT‑py‑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8.41％、8.02％、6.82％、6.12％，其热分解温度均达到了260℃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
本发明涉及四种含吡咯衍生物的聚合金属配合物染料敏化剂及其制备方法与用途，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
染料敏化剂作为DSSCs的核心组成部分而被广泛研究开发，因而已成为目前最具发展潜力的一类染料敏化剂。常用有机化合物苯并噻二唑等为辅助受体A’，但其存在拉电子能力受限等问题。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 型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、 BDTT-py-Cu和BDTT-py-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四种以苯并噻二吩联二噻吩衍生物 BDTT为给体(D)，以N-吡啶基-2-乙烯基吡咯与金属配位形成的配合物为辅助受体(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反应将给体和配合物连接而形成的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni，该类聚合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-py-Cd、BDTT-py-Zn、BDTT-py-Cu 和BDTT-py-Ni为染料敏化剂的电池光伏性能效率分别达到了8.41％、8.02％、6.82％、6.12％，其结构通式如下：
四种含吡咯衍生物的聚合金属配合物BDTT-py-Cd、 BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni的制备方法：
(1)N-吡啶基-2-甲酰吡咯的制备：
依次将3-溴吡啶、吡咯-2-甲醛、碳酸钾、碘化亚铜以及L-脯氨酸放入三口烧瓶中，3-溴吡啶与吡咯-2-甲醛的摩尔比为 1.4∶1.0～1.6:1.0，再加入DMSO作为溶剂，在110℃下，搅拌反应 36～72h，反应结束后加入水，用乙酸乙酯萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发仪除去溶剂得到粗产物，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯，其体积比为 0.9∶1.0～1.1∶1.0，得到淡黄色固体N-吡啶基-2-甲酰吡咯；
(2)N-吡啶基-2-乙烯基吡咯的制备：
取摩尔比为0.9∶1.0～1.1∶1.0的N-吡啶基-2-甲酰吡咯和甲基三苯基溴化鏻放入三口烧瓶中，加入精制的THF，分多批加入少量的氢化钠，氮气保护下升温至65℃，搅拌反应6～12h，冷却至室温，分别加入甲醇和蒸馏水，二氯甲烷萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发除去溶剂，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯，其体积比为9.0∶1.0～11.0∶1.0，得到深红色黏稠状液体N-吡啶基-2-乙烯基吡咯；
(3)5-甲酰-8-羟基喹啉的制备：
将8-羟基喹啉以及无水乙醇加入到三口烧瓶之中，通过搅拌溶解，再慢慢加入0.020～0.030mol的氢氧化钠溶液，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，待冷却至室温，旋转蒸发去除溶剂，倒入蒸馏水中，用浓盐酸与蒸馏水体积比1.0∶3.0～1.0∶5.0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；
(4)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
取摩尔比为1.0∶1.4～1.0∶1.6的5-甲酰-8-羟基喹啉和氰基乙酸放入三口烧瓶内，加入乙腈，搅拌使其溶解，依次加少量冰醋酸和哌啶，升温至85℃，搅拌反应24h以上，旋转蒸发除去少量溶剂，在 0℃下过夜，过滤干燥后用乙醇重结晶多次，得金黄色固体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(5)金属配合物py-Cd的制备：
取摩尔比为1.0∶1.8～1.0∶2.2的2-氰基-3-(8-羟基喹啉-5-基) 丙烯酸以及N-吡啶基-2-乙烯基吡咯加入到三口烧瓶中，取四氢呋喃加入其中，搅拌，将Cd(CH3COO)2·2H2O溶解在无水甲醇中，配制的溶液用恒压漏斗缓慢地滴加到烧瓶中，滴完后测pH，以保证反应体系为弱酸性，升温，回流反应10～16h，待混合物温度降至室温，过滤，固体分别用蒸馏水与无水乙醇洗涤数次，然后无水甲醇对所得固体重结晶，干燥数天，得橘黄色固体含镉配合物py-Cd；
(6)金属配合物py-Zn、py-Cd、py-Ni的制备：
配合物py-Zn、py-Cd、py-Ni的合成方法与配合物py-Cd的合成方法一致，将Cd(CH3COO)2·2H2O改为Zn(CH3COO)2·2H2O、 Cu(CH3COO)2·H2O、Ni(CH3COO)2·4H2O，分别得到黄色固体含锌配合物py-Zn、红棕色固体含铜配合物py-Cu、浅绿色固体含镍配合物 py-Ni；
(7)聚合金属配合物BDTT-py-Cd的合成：
取摩尔比为0.95～1.05∶1.00∶0.35～0.45∶0.20～0.30的配合物单体py-Cd、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)、催化剂Pd(CH3COO)2和三(2-甲苯基) 膦放入三口烧瓶中，然后加入少量的精制DMF溶剂以及除过水的三乙胺，在氮气氛围下，将温度升高到90℃并搅拌反应36～72h，反应结束后，将混合物静置到室温，过滤，固体用无水甲醇洗涤多次，得到的产物为黄色固体聚合镉金属配合物BDTT-py-Cd；
(8)聚合金属配合物BDTT-py-Zn、BDTT-py-Cu、BDTT-py-Ni 的合成：
聚合物(BDTT-py-Zn、BDTT-py-Cu、BDTT-py-Ni)的合成方法参照BDTT-py-Cd的合成，将反应需要的金属配合物(py-Cd)改为的金属配合物py-Zn、py-Cu、py-Ni，分别得到棕黑色固体产物聚合金属配合物BDTT-py-Zn、棕褐色固体产物聚合金属配合物BDTT-py-Cu、墨绿色固体产物聚合金属配合物BDTT-py-Ni。
四种D-A’-π-A型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、 BDTT-py-Zn、BDTT-py-Cu和BDTT-py-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)发明了四种新型含吡咯衍生物的聚合金属配合物，以苯并噻二吩联二噻吩衍生物BDTT为给体(D)，以N-吡啶基-2-乙烯基吡咯与金属配位形成的配合物为辅助受体 (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反应将给体和配合物连接，该配合物具有良好的光电转换效率和热稳定性，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N-吡啶基-2-甲酰吡咯的核磁共振氢谱(1H-NMR)(400MHz，CDCl3，ppm)；
图2本发明实施例合成的配体N-吡啶基-2-乙烯基吡咯的核磁共振氢谱(1H-NMR)(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(1H-NMR)(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(1H-NMR)(400MHz，CDCl3，ppm)；
图5本发明实施例合成的金属配合物py-Cd、py-Zn、py-Cu和 py-Ni的红外光谱(FT-IR)(KBr，cm-1)；
图6本发明实施例合成的化合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni的红外光谱(FT-IR)(KBr，cm-1)；
图7本发明实施例合成的化合物BDTT-py-Cd、BDTT-py-Zn、 BDTT-py-Cu和BDTT-py-Ni的热重分析曲线(TGA)；
图8本发明实施例合成的化合物BDTT-py-Cd、BDTT-py-Zn、 BDTT-py-Cu和BDTT-py-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-py-Cd、BDTT-py-Zn、 BDTT-py-Cu和BDTT-py-Ni的外量子效率(IPCE)曲线；
具体实施方式
本发明的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、 BDTT-py-Cu和BDTT-py-Ni的反应合成路线为：
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型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、 BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni，其分子结构式为：
上述聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu 和BDTT-py-Ni的制备方法：
A.N-吡啶基-2-甲酰吡咯的制备：依次将4.74g(30mmol)3-溴吡啶、1.9g(20mmol)吡咯-2-甲醛、5.52g(40mmol)碳酸钾、0.381g(2 mmol)碘化亚铜以及0.46g(4mmol)L-脯氨酸放入50ml三口烧瓶中，再加入30ml的DMSO作为溶剂，在110℃下，搅拌反应48h，反应结束后加入30ml水，用乙酸乙酯萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发仪除去溶剂得到粗产物，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯，其体积比为 1.0∶1.0，得到淡黄色固体1.29g，产率37.5％；m.p.77.2-78.1℃，核磁共振氢谱(1H-NMR)(CDCl3,ppm)见附图1,1H-NMR(CDCl3,ppm)：9.63(s,1H)，8.65-8.68(t,2H)，7.73-7.76(q,1H)，7.45(q,1H)，7.20-7.22 (t,1H)，7.11-7.12(d,1H)，6.49-6.51(t,1H).13C-NMR(CDCl3，ppm)： 111.59，123.39，124.96，131.55，132.27，133.62，135.67，146.56， 149.20，178.60.
B.N-吡啶基-2-乙烯基吡咯的制备：分别取0.96g(5.6mmol)N- 吡啶基-2-甲酰吡咯、2.22g(6.2mmol)甲基三苯基溴化鏻放入150ml 三口烧瓶中，加入100ml精制的THF，分多批加入0.8g(33mmol) 氢化钠，氮气保护下升温至65℃，搅拌反应8h，冷却至室温，分别加入100ml甲醇和100ml蒸馏水，二氯甲烷萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发除去溶剂，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯，其体积比为10.0∶1.0，得到0.38g深红色黏稠状液体，产率39.8％；核磁共振氢谱 (1H-NMR)(CDCl3,ppm)见附图2,1H-NMR(CDCl3,ppm)：5.00-5.15(d， 1H)，5.40-5.55(d，1H)，6.25-6.33(t，1H)，6.35-6.40(t，1H)，6.56-6.57 (q，1H)，6.81-6.82(t，1H)，7.38-7.41(q，1H)，7.62-7.65(m，1H)， 8.60-8.61(q，1H)，8.62-8.63(d，1H).13C-NMR(CDCl3，ppm)：108.17， 110.21，112.52，122.99，123.67，125.58，132.52，133.29，136.29， 147.10，148.32.
C.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3,1H-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.
D.2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：分别将1.038g(6 mmol)5-甲酰-8-羟基喹啉以及0.765g(9mmol)氰基乙酸放入50mL 三口烧瓶内，加入12mL乙腈，搅拌使其溶解，依次加3mL冰醋酸和5滴哌啶，升温至85℃，搅拌反应24h，旋转蒸发使混合物接近饱和状态，在冰浴下至产物沉淀析出，过滤干燥后得0.944g，产率为67％，用25％的乙醇重结晶三次，得金黄色固体，m.p. 200.3～201.5℃，核磁共振氢谱(1H-NMR)(CDCl3,ppm)见附图 4,1H-NMR(CDCl3,ppm):8.95-8.96(d,1H),8.87(s,1H),8.60-8.62(d, 1H),8.41-8.43(d,1H),7.69-7.72(q,1H),7.25-7.27(d,1H)，但是由于羟基和羧基上的活泼氢在核磁氢谱中无法表征出，因此通过以下表征证明目标产物已被成功合成；FT-IR(KBr,cm-1):3447(O-H),2222(C≡N), 1581(C＝C),1532(C＝N).13C-NMR(DMSO-d6,ppm):164.19,159.11, 150.01,149.44,138.67,132.67,132.56,131.15,128.71,123.93,118.86, 117.29,112.16,102.97.Anal.Calcd.for[C13H8N2O3]:C,65.00；H,3.36； N,11.66％.Found:C,64.64；H,3.44；N,11.56％；
E.含镉配合物py-Cd的制备：分别将0.384g(1.6mmol)2-氰基 -3-(8-羟基喹啉-5-基)丙烯酸以及0.544g(3.2mmol)N-吡啶基-2-乙烯基吡咯加入到50ml三口烧瓶中，取20ml四氢呋喃加入其中，搅拌，将0.426g(1.6mmol)Cd(CH3COO)2·2H2O溶解在6ml无水甲醇中，配制的溶液用恒压漏斗缓慢地滴加到烧瓶中，滴完后测pH，以保证反应体系为弱酸性，升温，回流反应12h，待混合物温度降至室温，过滤，固体分别用蒸馏水与无水乙醇洗涤三次，然后无水甲醇对所得固体重结晶，干燥数天，得0.692g橘黄色固体，产率为57％；红外谱图(FT-IR)(KBr,cm-1)见附图5，FT-IR(KBr,cm-1):3430(O-H),2211 (C≡N),1601(C＝C),1563(C＝N),1106(C-O-Cd),495(N-Cd).Anal. Calcd.for[C37H30N6O5Cd]:C,59.17；H,4.03；N,11.19.Found:C,59.04.； H,4.11；N,11.13％；
F.含锌配合物py-Zn的制备：配合物(py-Zn)的合成方法与配合物(py-Cd)的合成方法一致，将已合成的配合物Cd(CH3COO)2·2H2O 改为Zn(CH3COO)2·2H2O(0.305g，1.6mmol)，得到0.691g黄色固体，产率61％；红外谱图(FT-IR)(KBr,cm-1)见附图5，FT-IR(KBr,cm-1): 3430(O-H),2210(C≡N),1610(C＝C),1570(C＝N),1110(C-O-Zn),515 (N-Zn).Anal.Calcd.for[C37H30N6O5Zn]:C,63.12；H,4.29；N,11.94. Found:C,63.15；H,4.34；N,11.89％；
G.含铜配合物py-Cu的制备：配合物(py-Cu)的合成方法与配合物(py-Cd)的合成方法一致，将已合成的配合物Cd(CH3COO)2·2H2O 改为Cu(CH3COO)2·H2O(0.318g，1.6mmol)，得到0.593g红棕色固体，产率53％；红外谱图(FT-IR)(KBr,cm-1)见附图5，FT-IR(KBr, cm-1):3423(O-H),2212(C≡N),1621(C＝C),1562(C＝N),1116 (C-O-Cu),518(N-Cu).Anal.Calcd.for[C37H30N6O5Cu]:C,63.28；H, 4.31；N,11.97.Found:C,63.21；H,4.38；N,12.03％；
H.含镍配合物py-Ni的制备：配合物(py-Ni)的合成方法与配合物(py-Cd)的合成方法一致，将已合成的配合物Cd(CH3COO)2·2H2O 改为Ni(CH3COO)2·4H2O(0.397g，1.6mmol)，得到0.601g浅绿色固体，产率54％；红外谱图(FT-IR)(KBr,cm-1)见附图5，FT-IR(KBr, cm-1):3414(O-H),2210(C≡N),1563(C＝N),1107(C-O-Ni),502(N-Ni).Anal.Calcd.for[C37H30N6O5Ni]:C,63.73；H,4.34；N,11.47.Found:C, 63.68；H,4.39；N,11.51％；
I.聚合金属配合物BDTT-py-Cd的合成：分别将配合物单体py-Cd(0.226g,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)(0.221g,0.3mmol)、催化剂Pd(CH3COO)2(0.0027g,0.012mmol)和三(2-甲苯基)膦(0.0255g, 0.075mmol)放入25ml三口烧瓶中，然后加入精制的DMF溶剂7mL 以及除过水的三乙胺(3mL)，在氮气氛围下，将温度升高到90℃并搅拌反应48h，反应结束后，将混合物静置到室温，过滤，固体用无水甲醇洗涤三次，得到的产物为黄色固体0.236g，产率59％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3425(O-H), 2922,2850(C-H),2209(C≡N),1600(C＝C),1561(C＝N),1103(C-O- Cd),493(N-Cd).Anal.Calcd.for[C70H69N6O5S4Cd]:C,63.98；H,5.22； N,6.40；S,9.76.Found:C,63.73；H,5.48；N,6.27；S,9.83％.Mn＝11.79 Kg/mol,PDI＝1.93；
J.聚合金属配合物BDTT-py-Zn的合成：聚合物BDTT-py-Zn的合成方法参照BDTT-py-Cd的合成，将反应需要的含镉配合物(py-Cd) 改为0.211g(0.3mmol)的含锌配合物(py-Zn)，最终得到棕黑色固体产物0.202g，产率53％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3420(O-H),2960,2923,2853(C-H),2210(C≡N), 1660(C＝O),1600(C＝C),1560(C＝N),1106(C-O-Zn),509(N-Zn). Anal.Calcd.for[C70H69N6O5S4Zn]:C,66.36；H,5.41；N,6.63；S,10.12. Found:C,66.45；H,5.44；N,6.57；S,10.16％.Mn＝10.11Kg/mol,PDI＝2.04；
K.聚合金属配合物BDTT-py-Cu的合成：聚合物BDTT-py-Cu的合成方法参照BDTT-py-Cd的合成，将反应需要的含镉配合物(py-Cd) 改为0.210g(0.3mmol)的含铜配合物(py-Cu)，最终得到棕褐色固体产物0.183g，产率48％；红外谱图(FT-IR)(KBr,cm-1)见附图6，FT-IR(KBr,cm-1):3419(O-H),2925,2856(C-H),2207(C≡N),1618 (C＝C),1560(C＝N),1112(C-O-Cu),515(N-Cu).Anal.Calcd.for [C70H69N6O5S4Cu]:C,66.46；H,5.42；N,6.64；S,10.14.Found:C,66.51； H,5.51；N,6.58；S,10.21％.Mn＝12.62Kg/mol,PDI＝2.11。
L.聚合金属配合物BDTT-py-Ni的合成：聚合物(BDTT-py-Ni)的合成方法参照BDTT-py-Cd的合成，将反应需要的含镉配合物(py-Cd) 改为0.209g(0.3mmol)的含镍配合物(py-Ni)，最终得到墨绿色固体产物0.194g，产率51％；红外谱图(FT-IR)(KBr,cm-1)见附图6， FT-IR(KBr,cm-1):3397(O-H),2957,2924,2854(C-H),2209(C≡N), 1654(C＝O),1601(C＝C),1563(C＝N),1106(C-O-Ni),498(N-Ni). Anal.Calcd.for[C70H69N6O5S4Ni]:C,66.71；H,5.44；N,6.67；S,10.18. Found:C,66.81；H,5.49；N,6.61；S,10.13％.Mn＝10.05Kg/mol, PDI＝1.8。
实施例2：
测定聚合金属配合物染料BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-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基于聚合金属配合物的DSSCs的分子量测试数据
实施例3：
测定四种新型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、 BDTT-py-Zn、BDTT-py-Cu和BDTT-py-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；测定四种D-A’-π-A型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-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和外量子效率(IPCE)，其电池电流密度-电压(J-V)曲线如图8，外量子效率(IPCE)曲线见图9；；表2 是它们的光伏性能和光电转换效率测试结果；
表2基于含吡咯衍生物的聚合金属配合物的DSSCs的光伏性能数据
Claims (3)
1.四种D-A’-π-A型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni，其结构式如下：
2.根据权利要求1所述的四种D-A’-π-A型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-Ni的制备方法：
(1)N-吡啶基-2-甲酰吡咯的制备：
依次将3-溴吡啶、吡咯-2-甲醛、碳酸钾、碘化亚铜以及L-脯氨酸放入三口烧瓶中，3-溴吡啶与吡咯-2-甲醛的摩尔比为1.4∶1.0～1.6:1.0，再加入DMSO作为溶剂，在110℃下，搅拌反应36～72h，反应结束后加入水，用乙酸乙酯萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发仪除去溶剂得到粗产物，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯混合物，其体积比为0.9∶1.0～1.1∶1.0，得到淡黄色固体N-吡啶基-2-甲酰吡咯；
(2)N-吡啶基-2-乙烯基吡咯的制备：
取摩尔比为0.9∶1.0～1.1∶1.0的N-吡啶基-2-甲酰吡咯和甲基三苯基溴化鏻放入三口烧瓶中，加入精制的四氢呋喃，分多批加入少量的氢化钠，氮气保护下升温至65℃，搅拌反应6～12h，冷却至室温，分别加入甲醇和蒸馏水，二氯甲烷萃取，在有机相中加入无水硫酸镁，干燥过夜，过滤，旋转蒸发除去溶剂，粗产物经硅胶色谱柱分离纯化，展开剂为石油醚与乙酸乙酯混合物，其体积比为9.0∶1.0～11.0∶1.0，得到深红色黏稠状液体N-吡啶基-2-乙烯基吡咯；
(3)5-甲酰-8-羟基喹啉的制备：
将8-羟基喹啉以及无水乙醇加入到三口烧瓶之中，通过搅拌溶解，再慢慢加入0.020～0.030mol的氢氧化钠溶液，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，待冷却至室温，旋转蒸发去除溶剂，倒入蒸馏水中，用浓盐酸与蒸馏水体积比1.0∶3.0～1.0∶5.0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；
(4)2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：
取摩尔比为1.0∶1.4～1.0∶1.6的5-甲酰-8-羟基喹啉和氰基乙酸放入三口烧瓶内，加入乙腈，搅拌使其溶解，依次加少量冰醋酸和哌啶，升温至85℃，搅拌反应24h以上，旋转蒸发除去少量溶剂，在0℃下过夜，过滤干燥后用乙醇重结晶多次，得金黄色固体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸；
(5)金属配合物py-Cd的制备：
取摩尔比为1.0∶1.8～1.0∶2.2的2-氰基-3-(8-羟基喹啉-5-基)丙烯酸以及N-吡啶基-2-乙烯基吡咯加入到三口烧瓶中，取四氢呋喃加入其中，搅拌，将Cd(CH3COO)2·2H2O溶解在无水甲醇中，配制的溶液用恒压漏斗缓慢地滴加到烧瓶中，滴完后检测并调节pH值，以保证反应体系为弱酸性，升温，回流反应10～16h，待混合物温度降至室温，过滤，固体分别用蒸馏水与无水乙醇洗涤数次，然后无水甲醇对所得固体重结晶，干燥数天，得橘黄色固体含镉配合物py-Cd；
(6)金属配合物py-Zn、py-Cd、py-Ni的制备：
配合物(py-Zn、py-Cd、py-Ni)的合成方法与配合物(py-Cd)的合成方法一致，将Cd(CH3COO)2·2H2O改为Zn(CH3COO)2·2H2O、Cu(CH3COO)2·H2O、Ni(CH3COO)2·4H2O，分别得到黄色固体含锌配合物py-Zn、红棕色固体含铜配合物py-Cu、浅绿色固体含镍配合物py-Ni；
(7)聚合金属配合物BDTT-py-Cd的合成：
取摩尔比为0.95～1.05∶1.00∶0.35～0.45∶0.20～0.30的配合物单体py-Cd、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)、催化剂Pd(CH3COO)2和三(2-甲苯基)膦放入三口烧瓶中，然后加入少量的精制DMF溶剂以及除过水的三乙胺，在氮气氛围下，将温度升高到90℃并搅拌反应36～72h，反应结束后，将混合物静置到室温，过滤，固体用无水甲醇洗涤多次，得到的产物为黄色固体聚合镉金属配合物BDTT-py-Cd；
(8)聚合金属配合物BDTT-py-Zn、BDTT-py-Cu、BDTT-py-Ni的合成：
聚合物(BDTT-py-Zn、BDTT-py-Cu、BDTT-py-Ni)的合成方法参照BDTT-py-Cd的合成，将反应需要的镉金属配合物(py-Cd)改为金属配合物py-Zn、py-Cu和py-Ni，分别得到棕黑色固体产物聚合金属配合物BDTT-py-Zn、棕褐色固体产物聚合金属配合物BDTT-py-Cu、墨绿色固体产物聚合金属配合物BDTT-py-Ni。
3.根据权利要求1所述的四种D-A’-π-A型含吡咯衍生物的聚合金属配合物BDTT-py-Cd、BDTT-py-Zn、BDTT-py-Cu和BDTT-py-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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| CN110606937B (zh) * | 2018-06-14 | 2022-03-29 | 湘潭大学 | 一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物及其制备方法与用途 |
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