基于三吡啶烯烃配体的一维配位聚合物：合成、结构及光电性质  

One-Dimensional Coordination Polymers Based on a Tripyridine Olefin Ligand:Synthesis,Structures and Photoelectronic Properties

作　　者：陈慧娴 刘春玉 周璇 陈敏敏[1] 倪春燕[1] 郎建平[1] CHEN Hui-Xian;LIU Chun-Yu;ZHOU Xuan;CHEN Min-Min;NI Chun-Yan;LANG Jian-Ping(Suzhou Key Laboratory of Precision Transformation of Resource Molecules, College of Chemistry,Chemical Engineering and Materials Science, Soochow University, Suzhou, Jiangsu 215123, China)

机构地区：[1]苏州大学材料与化学化工学部苏州市资源分子精准转化重点实验室

出　　处：《无机化学学报》2019年第11期2038-2044,共7页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21531006,21773163);苏州市资源分子精准转化重点实验室(No.SZS201905)资助项目

摘　　要：在室温下,用三吡啶烯烃配体dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine(ppvppa)与银盐溶液反应,分别得到3个具有类似的一维链结构的配位聚合物{[Ag(ppvppa)]BF4}n(1)、{[Ag(ppvppa)]PF6}n(2)和{[Ag(ppvppa)]NO3}n(3)。在溶剂热条件下,用ppvppa与Ni(Ⅱ)反应,得到另一个以辅助羧酸配体桥联的一维配位聚合物{[Ni(ppvppa)(2,3-NDC)(H2O)]·2H2O}n(4)。对配合物1~4分别进行了元素分析、红外、热重、粉末X射线衍射、单晶X射线衍射等结构表征。配合物1~3呈现出由ppvppa连接Ag(Ⅰ)形成的阳离子一维双股链结构。配合物4呈现出由2,3-NDC配体桥联2个相邻的[Ni2(ppvppa)2(H2O)2]单元形成的中性一维双股链结构。含有Ag(Ⅰ)的配合物1~3表现出良好的荧光性质,而含Ni(Ⅱ)的配合物4没有荧光响应。选取配合物1和4作为代表,研究了它们的光电流响应性质。配合物1和4均表现出灵敏的阳极光电流响应,且在多次循环后仍保持稳定且可重复,其光电流值分别为2和6μA,明显强于空白ITO电极的光电流响应。The reactions of dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine(ppvppa) with various silver (Ⅰ)salts afforded three one-dimensional(1 D) coordination polymers {[Ag(ppvppa)]BF4}n(1), {[Ag(ppvppa)]PF6}n(2) and{[Ag(ppvppa)]NO3}n(3). When analogous reactions of ppvppa with Ni(Ⅱ) salt was carried out under solvothermal conditions, another 1 D coordination polymer {[Ni(ppvppa)(2,3-NDC)(H2 O)]·2 H2 O}n(4) was obtained. Complexes 1~4 were characterized by elemental analysis, infrared spectrum(IR), thermogravimetric analysis(TGA), powder X-ray diffraction(PXRD) and single crystal X-ray diffraction. Complexes 1 ~3 have similar 1 D cationic chain structures in which the dimeric [Ag(ppvppa)]2 units are interconnected by ppvppa ligands. Complex 4 holds a double chain structure in which the [Ni2(ppvppa)2(H2 O)2] units are interlinked by pairs of 2,3-NDC ligands. In the solid state, Ag(Ⅰ)-based complexes 1~3 showed good luminescent properties while no luminescence was observed for Ni(Ⅱ)-based complex 4. Complexes 1 and 4 as representative samples showed relatively prompt, rapid anodic photocurrent responses, which were steady and reproducible after ten on/off cycles. The photocurrent values were calculated to be 2 μA for 1 and 6 μA for 4, respectively, which were greater than that observed for a blank ITO electrode. CCDC: 1944469, 1;1944470, 2;1944471, 3;1944472, 4.

关 键 词：配位聚合物 晶体结构 荧光性质 光电流响应 

分 类 号：O614.122[理学—无机化学] O614.81[理学—化学]