Zhou Tao, Zhang Gengyi, Tan Chunhong, Liu Yong, Wang Xiao-Feng
School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China.
School of Resources Environment and Safety Engineering, University of South China, Hengyang 421001, China.
Molecules. 2025 Apr 28;30(9):1953. doi: 10.3390/molecules30091953.
The reaction of copper nitrate, phthalic acid (1,2-HBDC), and bipyridine in ammonia/ethanol media affords two multi-copper (II) cluster-based coordination polymers, namely {[Cu(bpy)(OH)(BDC)]·2OH·13HO} () and {[Cu(BDC)(bpy)(HO)]·3HO} (), under ambient conditions, with forming at the bottom and at the upper edge of the same beaker. The single-crystal structures reveal that it is a rare case of gradient-induced formation of different multi-copper(II) cluster-based CPs within a single-solution chemical reaction. crystallizes in the monoclinic system, sp. gr. 2/c, and is composed of chair-like tetranuclear [Cu(-OH)(bpy)(BDC)] clusters as secondary building units, bridged by BDC ligands to form a two-dimensional layer framework, while crystallizes in the monoclinic system, sp. gr. 2/n, with binuclear [Cu(1,2-BDC)(bpy)(HO)] clusters linked by bridging BDC ligands to form a one-dimensional looped double chain. Through intermolecular - stacking and hydrogen bonds between the coordination water, lattice water, and free oxygen atoms from carboxylate, both compounds yield a 3D supramolecular structure.
在氨/乙醇介质中，硝酸铜、邻苯二甲酸（1,2-苯二甲酸）和联吡啶反应，在环境条件下生成两种基于多铜（II）簇的配位聚合物，即{[Cu(bpy)(OH)(BDC)]·2OH·13HO}（）和{[Cu(BDC)(bpy)(HO)]·3HO}（），其中在同一个烧杯底部形成，在上边缘形成。单晶结构表明，在单溶液化学反应中梯度诱导形成不同的基于多铜（II）簇的配位聚合物是一种罕见的情况。以单斜晶系结晶，空间群为2/c，由椅状四核[Cu(-OH)(bpy)(BDC)]簇作为二级结构单元，通过BDC配体桥连形成二维层状骨架，而以单斜晶系结晶，空间群为2/n，双核[Cu(1,2-BDC)(bpy)(HO)]簇通过桥连BDC配体连接形成一维环状双链。通过配位水、晶格水和羧酸盐中游离氧原子之间的分子间堆积和氢键作用，两种化合物都形成了三维超分子结构。
