Mononuclear mercury(II) complexes containing bipyridine derivatives and thiocyanate ligands: Synthesis, characterization, crystal structure determination, and luminescent properties

Abstract

A series of mercury(II) complexes, [Hg(NN)(SCN)2] (NN is 4,4′-dimethyl-2,2′-bipyridine in 1, 5,5′-dimethyl-2,2′-bipyridine in 2, 6,6′-dimethyl-2,2′-bipyridine in 3 and 6-methyl-2,2′-bipyridine in 4), were prepared from the reactions of Hg(SCN)2 with mentioned ligands in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurement by methanol diffusion into a DMSO solution. The four complexes were thoroughly characterized by spectral methods (IR, UV–Vis, 13C{1H}NMR, 1H NMR and luminescence), elemental analysis (CHNS) and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the mercury(II) cation is four-coordinated in a distorted tetrahedral configuration by two S atoms from two thiocyanate anions and two N atoms from one chelating 2,2′-bipyridine derivative ligand. Also, in these complexes intermolecular interactions, for example CH⋯N hydrogen bonds (in 1–4), CH⋯S hydrogen bonds (in 1, 2 and 4), π … π interactions (in 2–4), Hg⋯N interactions (in 2) and S⋯S interactions (in 4), are effective in the stabilization of the crystal structures and the formation of the 3D supramolecular complexes. Furthermore, the luminescence spectra of the title complexes show that the intensity of their emission bands are stronger than the emission bands for the free bipyridine derivative ligands.