Marmier Mathieu, Cecot Giacomo, Vologzhanina Anna V, Bila José L, Zivkovic Ivica, Ronnow Henrik M, Nafradi Balint, Solari Euro, Pattison Philip, Scopelliti Rosario, Severin Kay
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland.
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia.
Dalton Trans. 2016 Oct 4;45(39):15507-15516. doi: 10.1039/c6dt02758j.
Dinuclear clathrochelate complexes with two, three, four, or five cyano groups in the ligand periphery were prepared following two distinct synthetic strategies: (a) zinc(ii)- or cobalt(ii)-templated polycondensation reactions of CN-functionalized arylboronic acids and phenoldioximes, or (b) postsynthetic cross-coupling reactions of polybrominated zinc(ii) clathrochelates with 4-cyanophenylboronic acid. The new clathrochelate complexes were used as metalloligands for the construction of heterometallic Zn/Ag and Co/Ag coordination polymers (CPs), which were characterized by single crystal X-ray diffraction and FT-IR. A one-dimensional CP was observed for ditopic clathrochelates, whereas two- and three-dimensional CPs were generated from tetra- and pentatopic metalloligands. The three-dimensional network is unique as it displays an unprecedented network topology with the point symbol (8·10)(8·10)(8·10)(8·10). Furthermore, it is a self-catenated net with an extremely high topological density.
通过两种不同的合成策略制备了在配体外围带有两个、三个、四个或五个氰基的双核笼形螯合物配合物：(a) 氰基官能化芳基硼酸与酚二肟的锌 (ii) 或钴 (ii) 模板缩聚反应，或 (b) 多溴化锌 (ii) 笼形螯合物与 4-氰基苯基硼酸的合成后交叉偶联反应。这些新型笼形螯合物配合物用作金属配体来构建异金属 Zn/Ag 和 Co/Ag 配位聚合物 (CPs)，通过单晶 X 射线衍射和傅里叶变换红外光谱对其进行了表征。对于双齿笼形螯合物观察到一维 CP，而二维和三维 CP则由四齿和五齿金属配体生成。三维网络很独特，因为它显示出具有点符号 (8·10)(8·10)(8·10)(8·10) 的前所未有的网络拓扑结构。此外，它是一个具有极高拓扑密度的自连环网络。
