Syntheses, Crystal Structures, and Properties of New Coordination Polymers Incorporating 3,3‐Dimethylcyclopropane‐1,2‐dicarboxylate and 4,4′‐Bipyridine Ligands

Three coordination polymers, [Zn(dcd)(bipy)0.5]n (1‐Zn), [Co(dcd)(bipy)0.5]n (2‐Co), and [Cu(bipy)2(H2O)1.5·(Hdcd)2·(H2O)3.5]4n (3‐Cu) (dcd = 3,3‐dimethylcyclopropane‐1,2‐dicarboxylate dianion, bipy = 4,4′‐bipyridine) were prepared by hydrothermal reactions. They were characterized by elemental analyses, FT‐IR spectra, single‐crystal X‐ray diffraction, X‐ray powder diffraction, photoluminescent and magnetic techniques. Single‐crystal X‐ray diffraction studies reveal that 1‐Zn and 2‐Co are isostructural and characteristic for 1D metal‐organic chains constructed by dcd bridging. Both of them contain mononuclear metal ions simultaneously bridged with short carboxylate bridges and long bipy spacers, resulting in a 2D grid framework. 3‐Cu is a neutral sandwiched ionic solid consisting of the positively charged trinuclear copper‐based coordination polymer and discrete Hdcd anions. 3‐Cu features two kinds of independent layers, which are further packed into a 3D supramolecular structure by strong hydrogen bonding interactions. Furthermore, 1‐Zn displays fluorescent emission assigned to the intra‐ligand fluorescence emission. Both 2‐Co and 3‐Cu exhibit antiferromagnetic coupling interactions. The carboxylate bridges existed in μ3‐dcd ligands can effectively mediate the antiferromagnetic interaction between CoII ions in 2‐Co, whereas strong hydrogen bonds are effective magnetic exchange pathways in 3‐Cu.