Synthesis, structure, photoluminescence and electrochemical properties of mononuclear Ag(I) and polymeric Zn(II) complexes of potassium 4-methyl piperazine-1-carbodithioate

Abstract

New heteroleptic mononuclear complex [Ag(mpdtc)(PPh3)2] (1) and homoleptic polymeric complex [Zn(mpdtc)2]n (2) have been synthesized from potassium 4-methyl piperazine-1-carbodithioate [K(mpdtc)]. The complexes have been characterized by elemental analyses, IR, NMR, UV–vis, thermal, cyclic voltammetry, and X-ray diffraction technique. Complexes 1 and 2 are fluorescent materials and exhibit emission maxima at around 32000 cm−1 upon excitation at 39000 cm−1. Thermogravimetric analysis of complexes as investigated by TG-DTA, suggests the formation of their respective metal sulfides as final thermally stable chemical entities. Electrochemical studies of silver(I) complex reveals the formation of silver nanoparticle which catalyses the oxidation of the ligand. The Ag(I) ion adopts a distorted tetrahedral geometry in complex 1 and the geometry around Zn(II) ion in complex 2 is in halfway between square planar and trigonal bipyramidal. The crystal structures of complexes are stabilized by intermolecular C-H…S interactions. © 2018 Elsevier B.V.