CN113321790B - 两个聚合亚胺衍生物合镉、镍配合物及其制备方法与用途 - Google Patents
两个聚合亚胺衍生物合镉、镍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所示的两个聚合亚胺衍生物合镉、镍配合物BDTT‑IM‑Cd、BDTT‑IM‑Ni及其制备方法与用途，它们以功能化的亚胺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Yamamoto反应合成的两个聚合亚胺衍生物合镉、镍配合物，实验基于以BDTT‑IM‑Cd、BDTT‑IM‑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9.61％、7.79％，其热分解温度均达到了270℃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
本发明涉及两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、 BDTT-IM-Ni及其制备方法与应用其为染料敏化剂的用途，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
从国内、国际对太阳能转换为电能的技术研究、开发和应用现状来看，染料敏化太阳能电池未来仍将是最具发展潜力和大规模化应用前景的清洁和可再生光电转化技术和世界光电材料领域中的一个顶尖高地，而决定染料敏化太阳能电池光电转化效率等光伏性能的最关键组分材料是染料敏化剂，因此，本项目选择设计与合成新型和具有发展潜力和前景的新型高光伏性能染料，是一个重要的主体科学研究发展方向，具有理论和实际应用价值和意义，本发明研究以吸电子能力强，且通过能调节配位键强度而能调节吸电子能力大小的亚胺衍生物合金属配合物做辅助电子受体A’，并将给体(D)连接受体部分 -A’-(π-A)2以增加受体部分的吸拉电子能力，而制备了两个聚合 D-A’-(π-A)2型亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-Ni 染料敏化剂，测试数据表明它们具有较好的吸光性能与光伏性能。
发明内容
本发明的目的是为提供和制备以苯并二噻吩联二噻吩衍生物BDTT为电子给体(D)，以功能化的亚胺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连接而合成的两个聚合 D-A’-(π-A)2型亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-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(PCE)和热稳定性，基于以BDTT-IM-Cd、BDTT-IM-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9.61％、7.79％，其结构通式如下：
两个聚合亚胺衍生物合镉、镍配合物的制备方法：
(1)(N4E，N4'E)-N4，N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'- 联苯]-4,4'-二胺的制备：
在两口烧瓶中加入摩尔比为0.6:2.0～1.5:2.0的二甲氧基联苯胺和对溴苯甲醛，然后加入少量无水乙醇，接着往烧瓶中加入少量无水硫酸镁，加热回流反应8～16h，反应停止后冷却至室温，旋转蒸发得粗产物，用无水乙醇冲洗三次，得到橙黄色固体；
(2)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，加入无水乙醇搅拌溶解，缓慢滴加少量氯仿，再向烧瓶中加入十六烷基三甲基溴化铵(CTMAB)， 8-羟基喹啉与CTMAB的摩尔比为1.2:3.0～2.0:3.0，然后在室温下缓慢滴加NaOH溶剂，升温回流反应8～16h，反应结束后冷却至室温，旋转蒸发除去溶剂，将一定量蒸馏水倒入经旋转蒸发后剩余的黑色粘稠固体中，用稀盐酸调pH值至弱酸性，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，用石油醚进行洗涤，之后用乙醇重结晶，得到橙黄色固体；
(3)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0.7:1.1～1.5:1.1，再用乙腈溶解，随后加冰醋酸并滴加少量的哌啶，升温至70～100℃，反应18～30h 后停止加热，旋转蒸发除去部分溶液，在-10～10℃条件下过夜；过滤，所得固体用氯仿冲洗数次，真空干燥，再用乙醇重结晶，得到金黄色固体产物；
(4)镉配合物IM-Cd的制备：
依次称取摩尔比为0.6:2.0～1.5:2.0的主配体(N4E，N4'E)-N4， N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'-联苯]-4,4'-二胺和辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入三口圆底烧瓶中，量取少量 THF到烧瓶，搅拌至固体溶解，固体全部溶解后，用分析天平精准称量Cd(CH3COO)2·2H2O固体，用无水甲醇溶解，并其缓慢加到反应瓶中，滴加完毕后，用三乙胺或者冰醋酸调节体系pH值至弱酸性，升温至回流反应18～30h，冷却至室温，用无水乙醇和去离子水洗涤三次后干燥，得到金黄色固体产物；
(5)镍配合物IM-Ni的制备：
此反应参照IM-Cd的合成方法，将Cd(CH3COO)2·2H2O改为 Ni(CH3COO)2·2H2O，经处理后得到黄绿色固体IM-Ni；
(6)聚合金属配合物BDTT-IM-Cd的制备：
在单口圆底烧瓶中依次加入摩尔比为0.6:1.0～1.5:1.0的Cd(II)配合物单体IM-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)，然后加入少量锌粉、三苯基磷、双(三苯基膦)二氯化镍以及2,2’-联亚胺，再加入少量DMF，在氮气保护下，回流反应40～56h，待反应结束后，冷却、过滤，用无水乙醇洗涤三次并干燥，得到金黄色固体BDTT-IM-Cd；
(7)聚合金属配合物BDTT-IM-Ni的制备：
聚合金属配合物BDTT-IM-Ni的具体合成方法参照BDTT-IM-Cd 的合成，将IM-Cd替换成IM-Ni，经过反应处理得到黄褐色固体产物 BDTT-IM-Ni；
两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-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)发明了两个聚合亚胺衍生物合镉、镍配合物，它们是以苯并噻二吩联二噻吩衍生物BDTT为电子给体 (D)，以功能化的亚胺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连接而合成的两个聚合D-A’-(π-A)2型亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-Ni染料敏化剂，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(N4E，N4'E)-N4，N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'-联苯]-4,4'-二胺的核磁共振氢谱(1HNMR) (400MHz，CDCl3，ppm)；
图2本发明实施例合成的中间体5-甲酰基-8-羟基喹啉的核磁共振氢谱(1HNMR)(400MHz，CDCl3，ppm)；
图3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4本发明实施例合成的金属配合物IM-Cd、IM-Ni的红外光谱 (FTIR)(KBr，cm-1)；
图5本发明实施例合成的聚合配合物BDTT-IM-Cd、 BDTT-IM-Ni的红外光谱(FTIR)(KBr，cm-1)；
图6本发明实施例合成的聚合配合物BDTT-IM-Cd、 BDTT-IM-Ni的热重分析曲线(TGA)；
图7本发明实施例合成的聚合配合物BDTT-IM-Cd、 BDTT-IM-Ni的紫外-可见吸收光谱(UV-vis)；
图8本发明实施例合成的聚合配合物BDTT-IM-Cd、 BDTT-IM-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聚合配合物BDTT-IM-Cd、 BDTT-IM-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
本发明的两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、 BDTT-IM-Ni的反应合成路线如式1-1：
下面结合具体实施例对本发明做进一步的说明
实施例1：
两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-Ni，其分子结构式如式1-2：
上述两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-Ni的制备方法：
A.(N4E，N4'E)-N4，N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'- 联苯]-4,4'-二胺的制备：在150mL两口烧瓶中加入3.05g(12.5mmol) 二甲氧基联苯胺和4.6g(25.0mmol)对溴苯甲醛，再加入50mL无水乙醇，加完后往烧瓶中加入5.0g无水硫酸镁，加热回流反应12h，反应停止后冷却至室温，旋转蒸发得粗产物，用无水乙醇多次冲洗，
式1-1两个亚胺聚合物的合成路线
得到橙黄色固体5.6g，产率78％，m.p.68-69℃，核磁共振氢谱(1H-NMR)见附图1，1H-NMR(CDCl3,ppm):8.57(s,2H,-CH＝N),7.82 (d,2H,Ar-H),7.65(d,2H,Ar-H),7.28(s,2H,Ar-H),7.25(d,2H,Ar-H),
式1-2两个亚胺聚合物的分子结构式
7.23(d,2H,Ar-H),4.00(d,6H,-CH3).13C-NMR(CDCl3,ppm):160.0, 153.0,142.2,138.5,135.4,131.7,128.5,125.4,123.8,121.5,113.0,55.8；
B.5-甲酰基-8-羟基喹啉的制备：向250mL三口烧瓶中加入25.0g (0.17mol)8-羟基喹啉，加入100mL无水乙醇搅拌溶解，缓慢滴加 25mL氯仿，再向烧瓶中加入0.100g(0.30mol)十六烷基三甲基溴化铵(CTMAB)搅拌，室温下缓慢滴加NaOH溶剂，滴加完将体系升温回流，反应12h，反应结束后冷却至室温，旋转蒸发除去溶剂后转移到1L的烧瓶中，再将500mL蒸馏水倒入旋转蒸发后剩余的黑色粘稠固体中，用10％的稀盐酸调pH值至弱酸性，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，用石油醚进行洗涤，之后用乙醇重结晶，得到橙黄色固体3.65g，产率12％，熔点为172～173℃，核磁共振氢谱见附图4，1H-NMR(CDCl3,ppm):10.14 (d,1H,-CHO),9.67(d,1H,Ar-H),8.87(d,1H,Ar-H),8.00(d,1H,Ar-H),7.65 (q,1H,Ar-H).13C-NMR(CDCl3,ppm):192.04,157.86,148.74,140.45,137.85,134.76,126.59,124.72,123.56,109.02；
C.2-氰基-3-(8-羟基喹啉-5-基)丙烯酸的制备：向干燥的250mL 三口烧瓶中依次加入5-甲酰基-8羟基喹啉1.74g(10.0mmol)和氰基乙酸1.39g(11.0mmol)，然后加入100mL乙腈，搅拌使固体溶解，随后加入10mL冰醋酸，最后用滴管滴加40滴哌啶，加热回流反应24h，停止反应后冷却至室温，旋转蒸发至析出沉淀，将固体干燥得到粗产物，用25％乙醇重结晶三次，得到橘黄色固体产物1.026g，产率64％，核磁共振氢谱见附图5，1H-NMR(DMSO-d6,ppm):8.96(s, 1H,Ar-H),8.91(s,1H,Ar-H),8.62(d,1H,Ar-H),8.42(d,1H,Ar-H),7.71(d,1H,Ar-H),7.26(d,1H,Ar-H).羟基和羧基上的活泼氢在核磁氢谱中无法表征出，但可通过以下表征证明目标产物成功合成，FTIR(KBr, cm-1):3447(-OH),2221(C≡N),1580(C＝C),1530(C＝N).13C-NMR (DMSO-d6,ppm):164.19,159.11,150.01,149.44,138.67,132.67,131.15,128.71,123.93,118.86,117.29,112.16,102.97..Anal.Calcd.for [C13H8N2O3]:C,65.00；H,3.36；N,11.66％.Found:C,64.74；H,3.44；N, 11.46％；
D.镉配合物IM-Cd的制备：依次称取主配体(N4E，N4'E)-N4， N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'-联苯]-4,4'-二胺2.89g(5.00 mmol)、辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸2.52g(10.5mmol) 加入500mL三口圆底烧瓶中，量取100mL THF，搅拌至固体溶解，等到固体全部溶解掉之后，用分析电子天平精准的称量 Cd(CH3COO)2·2H2O2.68g(10.5mmol)，用75mL无水甲醇溶解，将其缓慢加到反应瓶中，滴加完毕后，用三乙胺或者冰醋酸调节体系 pH值至弱酸性，升温至75℃，回流反应24h，冷却至室温，用无水乙醇和去离子水多次洗涤后干燥，得到了金黄色固体产物4.02g，产率68％，熔点在300摄氏度以上，红外谱图(FTIR)见附图4，FTIR (KBr,cm-1):3434(-OH),2209(C≡N),1617(C＝C),1557(C＝N),1108 (C-O-Cd),491(N-Cd).Anal.Calcd.for[C58H46CdN6O10Br2]:C,55.32；H, 3.66；N,6.68％.Found:C,53.72；H,3.99；N,6.92％；
E.镍配合物IM-Ni的制备：此反应参照IM-Cd的合成方法，将 Cd(CH3COO)2·2H2O改为2.142g(10.5mmol)Ni(CH3COO)2·2H2O，最终得到黄绿色固体产物3.53g，产率64％，熔点在300摄氏度以上，红外谱图(FTIR)见附图4，FTIR(KBr,cm-1):3421(-OH),2216(C≡N),1612(C＝C),1570(C＝N),1116(C-O-Ni),501(N-Ni).Anal.Calcd.for [C58H46NiN6O10Br2]:C,57.76；H,3.82；N,6.97％.Found:C,57.15；H, 3.22；N,6.43％；
F.聚合金属配合物BDTT-IM-Cd的制备：聚合物(BDTT-IM-Cd) 是根据yamamoto聚合反应而合成的，在150mL单口圆底烧瓶中依次加入2.395g(2.0mmol)Cd(II)配合物单体IM-Cd，1.53g(2.0mmol) 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)，0.65g(10mmol)锌粉，1.05g(4.0mmol)三苯基磷，1.3g(2.0mmol)双(三苯基膦)二氯化镍以及0.03g(0.19mmol) 2,2’-联亚胺，再加入75mL DMF，氮气保护下，回流反应48h，反应结束后，过滤，用无水乙醇充分洗涤并干燥得金黄色固体产物1.4g，产率48％，红外谱图(FTIR)见附图5，FTIR(KBr,cm-1):3375(-OH), 2927,2861(C-H),2203(C≡N),1602(C＝C),1557(C＝N),1104 (C-O-Cd),490(N-Cd).Anal.Calcd.for[C94H79N6O10S4Cd]:C,66.71；H, 4.67；N,4.97；S,7.60.Found:C,66.02；H,4.692；N,4.88；S,7.70％. Mn＝8.20×103g/mol,PDI＝2.35；
G.聚合金属配合物BDTT-IM-Ni的制备：此反应参照BDTT-IM-Cd的合成方法，将2.0mmol Cd(II)配合物IM-Cd换成2.29 g(2.0mmol)Ni(II)配合物IM-Ni，与BDTT 1.53g(2.0mmol)反应，经处理获得黄褐色固体1.29g，产率55％，红外谱图(FTIR)见附图 5，FTIR(KBr,cm-1):3421(-OH),2934.2861(C-H),2211(C≡N),1611 (C＝C),1563(C＝N),1113(C-O-Ni),496(N-Ni).Anal.Calcd.for [C94H79N6O10S4Ni]:C,68.86；H,4.82；N,5.13；S,7.81％.Found:C, 68.22；H,4.23；N,5.46；S,7.12％.Mn＝10.26×103g/mol,PDI＝1.82。
实施例2：
测定两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、 BDTT-IM-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6。
实施例3：
测定两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、 BDTT-IM-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watersstyragel columns(103，104，
)，柱温箱温度80℃，以DMF为流动相，PS溶液作参比，流速为1.00mL/min进行测试，测试结果如表1。
表1两个聚合亚胺衍生物合镉、镍配合物的分子量测试数据
实施例4：
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Keithley2400数字源表改变电压并记录电流随电压的变化值；IPCE测试由Oriel Cornerstone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；
表2两个聚合亚胺衍生物合镉、镍配合物的光伏性能测试数据
测定以两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、 BDTT-IM-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。
Claims (2)
1.两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-Ni，其结构式如下：
如上所述的两个聚合亚胺衍生物合镉、镍配合物的制备方法：
(1)(N4E，N4'E)-N4，N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'-联苯]-4,4'-二胺的制备：
在两口烧瓶中加入摩尔比为0.6:2.0～1.5:2.0的二甲氧基联苯胺和对溴苯甲醛，然后加入少量无水乙醇，接着往烧瓶中加入少量无水硫酸镁，加热回流反应8～16h，反应停止后冷却至室温，旋转蒸发得粗产物，用无水乙醇冲洗三次，得到橙黄色固体；
(2)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，加入无水乙醇搅拌溶解，缓慢滴加少量氯仿，再向烧瓶中加入十六烷基三甲基溴化铵(CTMAB)，8-羟基喹啉与CTMAB的摩尔比为1.2:3.0～2.0:3.0，然后在室温下缓慢滴加NaOH溶剂，升温回流反应8～16h，反应结束后冷却至室温，旋转蒸发除去溶剂，将一定量蒸馏水倒入经旋转蒸发后剩余的黑色粘稠固体中，用稀盐酸调pH值至弱酸性，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，用石油醚进行洗涤，之后用乙醇重结晶，得到橙黄色固体；
(3)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0.7:1.1～1.5:1.1，再用乙腈溶解，随后加冰醋酸并滴加少量的哌啶，升温至70～100℃，反应18～30h后停止加热，旋转蒸发除去部分溶液，在-10～10℃条件下过夜；过滤，所得固体用氯仿冲洗数次，真空干燥，再用乙醇重结晶，得到金黄色固体产物；
(4)镉配合物IM-Cd的制备：
依次称取摩尔比为0.6:2.0～1.5:2.0的主配体(N4E，N4'E)-N4，N4'-双(4-溴亚苄基)-3,3'-二甲氧基-[1,1'-联苯]-4,4'-二胺和辅助配体2-氰基-3-(8-羟基喹啉-5-基)丙烯酸加入三口圆底烧瓶中，量取少量THF到烧瓶，搅拌至固体溶解，固体全部溶解后，用分析天平精准称量Cd(CH3COO)2·2H2O固体，用无水甲醇溶解，并其缓慢加到反应瓶中，滴加完毕后，用三乙胺或者冰醋酸调节体系pH值至弱酸性，升温至回流反应18～30h，冷却至室温，用无水乙醇和去离子水洗涤三次后干燥，得到金黄色固体产物；
(5)镍配合物IM-Ni的制备：
此反应参照IM-Cd的合成方法，将Cd(CH3COO)2·2H2O改为Ni(CH3COO)2·2H2O，经处理后得到黄绿色固体IM-Ni；
(6)聚合金属配合物BDTT-IM-Cd的制备：
在单口圆底烧瓶中依次加入摩尔比为0.6:1.0～1.5:1.0的Cd(II)配合物单体IM-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)，然后加入少量锌粉、三苯基磷、双(三苯基膦)二氯化镍以及2,2’-联亚胺，再加入少量DMF，在氮气保护下，回流反应40～56h，待反应结束后，冷却、过滤，用无水乙醇洗涤三次并干燥，得到金黄色固体BDTT-IM-Cd；
(7)聚合金属配合物BDTT-IM-Ni的制备：
聚合金属配合物BDTT-IM-Ni的具体合成方法参照BDTT-IM-Cd的合成，将IM-Cd替换成IM-Ni，经过反应处理得到黄褐色固体产物BDTT-IM-Ni。
2.根据权利要求1所述的两个聚合亚胺衍生物合镉、镍配合物BDTT-IM-Cd、BDTT-IM-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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