An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex ([CoCO3(bipy)2]2[Co(DCA)2]⋅16H2O) with two novel water tapes

Abstract

An unprecedented mixed valence cobalt(III)/cobalt(II) ion-pair complex, [CoCO3(bipy)2]2[Co(DCA)2]⋅16H2O (1) [bipy = 2,2′-bipyridine, DCA = demethylcantharidate, exo-1,4-epoxy-cyclohexyl-2,3-dicarboxylate group, (C8H8O5)2 −], has been synthesized and characterized by elemental analysis, IR, UV–vis, Thermogravimetric analysis (TGA) and single crystal X-ray diffraction. The crystal structure of 1 consists of three independent molecular moieties: [CoCO3(bipy)2]+, [Co(DCA)2]2–, and water molecules of crystallization. Interestingly, two novel water tapes, one comprises of alternate cyclic water tetramer and octamer, the other is constructed by alternate cyclic water hexamer and carboxylate–water hybrid octamer [(H2O)2(COO)2]2 −, have been detected for the first time in the host framework of 1. The two novel water tapes are linked together by the DCA and carbonate ligands via hydrogen bonds into a 2D water layer, and then the water layers assemble complex ions ([CoCO3(bipy)2]+ and [Co(DCA)2]2 −) through hydrogen bonds, π–π interactions and electrostatic interactions to form the overall 3D metal–organic framework structure.