A series of novel luminescent dinuclear zinc(II) diimine complexes with bridging chalcogenolate ligands have been synthesized, in which the two zinc atoms were found to exist in different coordination environment. The luminescence and electrochemical behavior of these complexes have been studied. These complexes have also been shown to exhibit dynamic fluxional behavior in solution due to an exchange of the bridging and terminal thiolate ligands. The mechanism and kinetics of which have been investigated by variable-temperature H-1 NMR studies. The X-ray crystal structure of [(bpy)Zn-2(SC6H4-Cl-p)(mu -SC6H4-Cl-p)(mu -OAc)(2)] has also been determined.