Supramolecular networks constructed by cationic copper(II) complexes incorporating hybrid water–anionic polymeric assemblies

Abstract

Two complexes, [Cu2(TFSA)(2,2′-bpy)4] · TFSA · 8H2O (1) and {[Cu(4,4′-bpy)(H2O)2] · TFSA · 6H2O} n (2) (H2TFSA = tetrafluorosuccinic acid, 2,2′-bpy = 2,2′-bipyridine, and 4,4′-bpy = 4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2−} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2−} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O ··· (H2O)6 ··· H2O−] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.