Zhou Xin, Li Yanger, Li Xin, Du Shengliang, Yang Yan, Xiong Kecai, Xie Yan, Shi Xinyu, Gai Yanli
School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116, P. R. China.
College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, Shandong 252059, P. R. China.
Inorg Chem. 2022 Aug 1;61(30):11687-11694. doi: 10.1021/acs.inorgchem.2c01273. Epub 2022 Jul 19.
A multifunctional Cd-based coordination polymer based on a viologen derivative and a secondary carboxylic ligand, namely, {[Cd(bcbp)(pta) (HO)]·2HO} (, HbcbpCl = 1,1'-bis(4-carboxyphenyl)-(4,4'-bipyridinium) dichloride, Hpta = -phthalic acid), has been solvothermally synthesized and structurally characterized. Compound is a 3D framework built on {Cd(pta) (HO)} net with square channels which intalls bcbp ligands at the diagonal position of the two adjacent square channels. Notably, compound exhibits a reversible photochromic transformation between yellowish gray and dark green under xenon light irradiation, which should be attributed to the formation of free viologen radicals. Furthermore, compound also displays a chemochromic phenomenon from yellowish gray to dark green after exposure to ammonia and hydrazine, which could be ascribed to the generation of viologen radicals and charge-transfer complexes triggered by nucleophilic attack of electron-rich ammonia and hydrazine molecules to the electron-deficient viologen moiety in the bcbp ligand. Moreover, compound is capable of quickly and selectively detecting MnO with a high quenching coefficient and a low limit of detection via a luminescent quenching process caused by the competitive absorption of excitation energy.
一种基于紫精衍生物和仲羧酸配体的多功能镉基配位聚合物，即{[Cd(bcbp)(pta)(H₂O)]·2H₂O}（HbcbpCl = 1,1'-双(4-羧基苯基)-(4,4'-联吡啶鎓)二氯化物，Hpta = 邻苯二甲酸），已通过溶剂热法合成并进行了结构表征。化合物是基于{Cd(pta)(H₂O)}网络构建的三维框架，具有方形通道，bcbp配体安装在两个相邻方形通道的对角位置。值得注意的是，化合物在氙灯照射下呈现出黄灰色和深绿色之间的可逆光致变色转变，这应归因于游离紫精自由基的形成。此外，化合物在暴露于氨和肼后也表现出从黄灰色到深绿色的化学变色现象，这可归因于富电子的氨和肼分子对bcbp配体中缺电子的紫精部分的亲核攻击引发的紫精自由基和电荷转移复合物的产生。此外，化合物能够通过由激发能量的竞争吸收引起的发光猝灭过程，以高猝灭系数和低检测限快速且选择性地检测MnO₄⁻。
