Li Jin-Yan, Yan Zheng, Ni Zhao-Ping, Zhang Ze-Min, Chen Yan-Cong, Liu Wei, Tong Ming-Liang
Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University , Guangzhou 510275, People's Republic of China.
Inorg Chem. 2014 Apr 21;53(8):4039-46. doi: 10.1021/ic403069d. Epub 2014 Mar 31.
Porous and nonporous 3D heterobimetallic coordination polymers based on the 1,4-di(pyridin-4-yl)benzene ligand (dpb), [Fe(dpb){Ag(CN)2}{Ag2(CN)3}]·nSolv (1·nSolv; nSolv = DMF·EtOH, 2DMF·MeCN) and [Fe(dpb)2{Ag(CN)2}2] (2), have been synthesized by diffusion technique, respectively. Single-crystal X-ray analysis shows that 1·nSolv consists of a 3D self-penetrating network with in-situ-generated Ag2(CN)3 species and displays one of the largest volume values of porosity (299 Å(3) per iron atom) after desolvation for the Hoffman-like porous SCO coordination polymers to date. In contrast, nonporous compound 2 is composed of two independent interpenetrated 3D nets with in-situ-generated Ag(dpb)(CN)2 species. Their significant distinctions of structural architectures lead to dramatically different magnetic properties: 1·nSolv displays two-step guest-effected SCO with hysteresis, whereas 2 presents characteristic paramagnetic behavior.
基于1,4 - 二（吡啶 - 4 - 基）苯配体（dpb）的多孔和无孔3D异双金属配位聚合物[Fe(dpb){Ag(CN)2}{Ag2(CN)3}]·nSolv（1·nSolv；nSolv = DMF·EtOH，2DMF·MeCN）和[Fe(dpb)2{Ag(CN)2}2]（2），已分别通过扩散技术合成。单晶X射线分析表明，1·nSolv由具有原位生成的Ag2(CN)3物种的3D自穿透网络组成，并且在脱溶剂后显示出霍夫曼类多孔SCO配位聚合物迄今为止最大的孔隙率体积值之一（每个铁原子299 Å(3)）。相比之下，无孔化合物2由两个具有原位生成的Ag(dpb)(CN)2物种的独立互穿3D网络组成。它们显著不同的结构架构导致了截然不同的磁性：1·nSolv表现出具有滞后的两步客体影响的SCO，而2呈现出特征性的顺磁行为。
