作　　者： (杜香莎）; (李海洋）; (刘恒）; (李根恒）; (李林科）; (臧双全）;

机构地区： 郑州大学化学与分子工程学院,郑州450001

出　　处： 《应用化学》 2017年第9期1024-1034,共11页

摘　　要： 利用紫精功能化的配体1-(3,5-二羧基苄基)-4,4'-联吡啶硝酸盐(H_2L^+NO_3^-)与Eu(Ⅲ)离子在溶剂热条件下得到一个金属有机配合物{[Eu(μ_2-OH)(L)(HCO_2)]·H_2O}_n(1),其中甲酸阴离子来自于溶剂DMF(N,N'-二甲基甲酰胺)分子的原位分解。单晶X射线衍射表明配合物1是一个手性的二维层状结构。配合物1呈现出可逆的、快速响应的光致变色特性。在光热作用下,它表现为肉眼可见的从浅黄到深绿色的可逆颜色改变,这种着色/脱色过程可以循环多次,具有很好的可逆性。结构分析表明,供体羧酸基团和受体紫精单元之间以及配合物中π···π相互作用为电子转移提供了有效的路径,从而导致光致变色行为的发生。该手性配合物不仅呈现出光调节荧光特性,还具有二阶非线性光学(SHG)开关性质。在相同粒径的测试条件下,配合物1的SHG信号强度大约是磷酸二氢钾(KDP)的3.8倍。此外,配合物1的表面光电压测定显示它呈现出光电活性。 The solvothermal reaction of a viologen-functionalized aromatic dicarboxylate ligand 1-（3,5- dicarboxybenzyl）-4,4＇-bipyridinium nitrate（ H2L＋ NO3- ） with Eu（ Ⅲ ） leads to the formation of a new metal-organic complex { [Eu（μ2-OH） （L） （HCO2） ] .H2O｜ n（1）, in which the formate anions come from the in situ decomposition of solvent dimethylformamide（DMF）. Single-crystal X-ray analysis revealed that complex I has chirality and diaplays a two-dimensional layer structure. Complex 1 manifests fast photoresponsive and reversibile photochromic properties. It gives an eye-detectable color change from pale-yellow to dark green upon exposure to light, and the coloring/fading processes can repeat several cycles. The structural analysis demonstrated that the electrons transfer from carboxylate donors to viologen acceptor as well as the π-π interaction offers reasonable electron-transfer pathways for the photochromic process. Interestingly, the synthesized solid-state chiral crystalline material not only exhibits tunable luminescence in response to light, but also shows photoswitching nonlinear optical （NLO） activity, and the second- harmonic generation（SHG） efficiency is approximately 3. 8 times that of potassium dihydrogen phosphate（KDP） in the same particle size. Moreover, surface photovoltage spectroscopy（SPS） of complex I has been investigated and the result indicates it exhibits interesting photovoltaic activity.

关 键 词： 紫精 配合物 荧光开关 非线性光学特性 光电活性