Wang Ning, Long Bing-Fan, Yin Xian-Hong, Huang Zhong-Jing, Mi Yan, Hu Fei-Long, Young David James
Key Laboratory of Chemistry and Engineering of Forest Products, State Ethnic Affairs Commission, Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Guangxi Collaborative Innovation Center for Chemistry and Engineering of Forest Products, Guangxi University for Nationalities, Nanning 530006, China.
College of Engineering, IT and Environment, Charles Darwin University, Darwin, NT 0909, Australia.
Dalton Trans. 2021 Dec 14;50(48):18194-18201. doi: 10.1039/d1dt03405g.
Four structurally diverse coordination polymers 1-4 (CP1-CP4) were designed and constructed from Cd(II) ions and various carboxyl ligands (Hoba, 4,4'-oxydibenzoic acid; Hbpa, ()-4,4'-(ethene-1,2-diyl)dibenzoic acid; Hpbda, 4,4'-((1,3-phenylenebis(methylene))bis(oxy))dibenzoic acid) and the alkene containing ligand (CH-bpeb, 4,4'-((1,1')-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))dipyridine). CP1-CP4 possess Cd binuclear secondary building units (SBUs). The geometry of the dicarboxylate ligands and the reaction conditions determined the final structure with a variety of motifs. CP1 possesses an interdigitated 2D structure, while CP2 consists of a 1D channel-like motif with isolated CH-bpeb molecules embedded in the channels. The solid-state structure of CP3 consists of two unique layers interpenetrated to form a 2D + 2D → 2D polycatenated backbone, while a 1D channel-like motif filled by isolated CH-bpeb molecules was observed for CP4. In all four coordination polymers pairs of CH-bpeb molecules were bound or encapsulated by the Cd secondary building units at an appropriate distance and orientation for solid-state [2 + 2] photodimerization of one pair of CC bonds. Desolvation of CP3 with heat resulted in a decrease in solid-state fluorescence and a slowing of the rate of solid-state photodimerization.
利用镉（II）离子与多种羧基配体（Hoba，4,4'-氧化二苯甲酸；Hbpa，（）-4,4'-（乙烯-1,2-二基）二苯甲酸；Hpbda，4,4'-（（1,3-亚苯基双（亚甲基））双（氧基））二苯甲酸）以及含烯烃配体（CH-bpeb，4,4'-（（1,1'）-（2,5-二甲基-1,4-亚苯基）双（乙烯-2,1-二基））二吡啶）设计并构建了四种结构不同的配位聚合物1-4（CP1-CP4）。CP1-CP4具有镉双核二级结构单元（SBUs）。二羧酸配体的几何结构和反应条件决定了具有多种结构基元的最终结构。CP1具有相互穿插的二维结构，而CP2由一维通道状结构基元组成，通道中嵌入了孤立的CH-bpeb分子。CP3的固态结构由两个独特的层相互贯穿形成二维 + 二维→二维多连锁骨架，而CP4则观察到由孤立的CH-bpeb分子填充的一维通道状结构基元。在所有四种配位聚合物中，CH-bpeb分子对以适当的距离和取向被镉二级结构单元结合或包封，用于一对CC键的固态[2 + 2]光二聚化。对CP3进行加热去溶剂化导致固态荧光减弱以及固态光二聚化速率减慢。
