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
作者单位E-mail
陈慧娴 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, 苏州 215123  
刘春玉 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, 苏州 215123 928483592@qq.com 
周璇 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, 苏州 215123  
陈敏敏 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, 苏州 215123  
倪春燕 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, 苏州 215123 chunyan89.ok@163.com 
郎建平 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, 苏州 215123 jplang@suda.edu.cn 
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}n1)、{[Ag(ppvppa)]PF6}n2)和{[Ag(ppvppa)]NO3}n3)。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}n4)。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14作为代表,研究了它们的光电流响应性质。配合物14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6 μA,明显强于空白ITO电极的光电流响应。
关键词: 配位聚合物  晶体结构  荧光性质  光电流响应
基金项目: 国家自然科学基金(No.21531006,21773163)和苏州市资源分子精准转化重点实验室(No.SZS201905)资助项目
Abstract: The reactions of dipyridin-2-yl-(4-(2-pyridin-4-yl-vinyl)-phenyl)-amine (ppvppa) with various silver(Ⅰ) salts afforded three one-dimensional (1D) 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 1D coordination polymer {[Ni(ppvppa)(2,3-NDC)(H2O)]·2H2O}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 1D 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(H2O)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.
Keywords: coordination polymers  crystal structures  fluorescence properties  photocurrent responses
投稿时间:2019-08-02 修订日期:2019-09-12
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陈慧娴,刘春玉,周璇,陈敏敏,倪春燕,郎建平.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[J].无机化学学报,2019,35(11):2038-2044.
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Support information: 相关附件:   file190384_Supporting_information_for_Publication_(re-revised).pdf