Syntheses, Crystal Structures, and Properties of Four Metal–Organic Complexes Based on 1,4,5,6,7,7-Hexachlorobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic Acid

Four metal–organic complexes [Ni­(HET)­(phen)­(H2O)]­·(HET)­·H2O (1), [Cu­(HET)­(phen)­(H2O)]­·1.5H2O (2), [Cu2(HET)2­(bipy)1.5­(H2O)]­·15DMF·2H2O (3), and [Cd2O­(HET)2­(bipy)­(H2O)]­·2H2O­·EtOH (4) (HET = 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]­hept-5-ene-2,3-dicarboxylic acid, phen = 1,10-phenanthroline, bipy = 4,4′-bipyridine) have been synthesized via hydro- or solvothermal reactions. It was found that complexes 1 and 2 are two-dimensional (2D) structures built from discrete complexes via the typical intermolecular interactions, and there was a closed loop built from the lattice water and carboxylate groups in 1 through intramolecular hydrogen bonds. Complex 3 exhibits three-dimensional (3D) structure with 5-connected bnn hexagonal BN topology. Complex 4 features a non-interpenetrating sql 2D coordination network, which is further linked into a 3D structure by C–H···Cl weak interaction. The properties of magnetism, fluorescence, and electrochemistry have also been investigated in this paper.