Zhang Cui-Juan, Chen Zi-Wei, Lin Rong-Guang, Zhang Ming-Jian, Li Pei-Xin, Wang Ming-Sheng, Guo Guo-Cong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou, Fujian 350002, People's Republic of China.
Inorg Chem. 2014 Jan 21;53(2):847-51. doi: 10.1021/ic402182j. Epub 2013 Dec 23.
The model compound [Zn(HCOO)2(4,4'-bipy)] (1; 4,4'-bipy = 4,4'-bipyridine) is selected in this work to demonstrate the effectiveness of our previously proposed design strategy for electron-transfer photochromic metal-organic complexes. The electron-transfer photochromic behavior of 1 has been discovered for the first time. Experimental and theoretical data illustrate that the photochromism of 1 can be attributed to the electron transfer from formato to 4,4'-bipy and the formation of a radical photoproduct. The electron transfer prefers to occur between formato and 4,4'-bipy, which are combined directly by the Zn(II) atoms. A high-contrast (up to 8.3 times) photoluminescence switch occurs during the photochromic process. The similarity of photochromic behaviors among 1 and its analogues as well as viologen compounds has also been found. Photochromic studies of this model compound indicate that new electron-transfer photochromic metal-organic complexes can be largely designed and synthesized by the rational assembly of nonphotochromic electron-donating and electron-accepting ligands.
在本工作中选择模型化合物[Zn(HCOO)₂(4,4'-bipy)] (1；4,4'-bipy = 4,4'-联吡啶)来证明我们之前提出的用于电子转移光致变色金属有机配合物的设计策略的有效性。首次发现了1的电子转移光致变色行为。实验和理论数据表明，1的光致变色可归因于从甲酸根到4,4'-联吡啶的电子转移以及自由基光产物的形成。电子转移更倾向于在直接由Zn(II)原子结合的甲酸根和4,4'-联吡啶之间发生。在光致变色过程中会出现高对比度（高达8.3倍）的光致发光开关。还发现了1与其类似物以及紫精化合物之间光致变色行为的相似性。对该模型化合物的光致变色研究表明，通过合理组装非光致变色的供电子和吸电子配体，可以大量设计和合成新的电子转移光致变色金属有机配合物。
