Terpyridine–tetrathiafulvalene hybrid ligands and their electroactive metal complexes

Abstract
The synthesis and full characterization (including X-ray structures) of two redox-active terpyridine–tetrathiafulvalene ligands namely (4′-amido-2,2′:6′,2′′-terpyridyl)-6,7-ethylenedithiotetrathiafulvalene (1) and 2-(4′-thioacetamide-2,2′:6′,2′′-terpyridyl)-3,6,7-tris(methylsulfanyl)-6,tetrathiafulvalene (2) are described. The binding properties of these multifunctional systems for various transition metal cations (Ni2+, Zn2+, Cd2+ and Fe2+) are analyzed in solution by cyclic voltammetry and UV-visible spectroscopy. In addition, a tetrahedral neutral zinc metal complex of ligand (2) formulated as (MeS)3-TTF-SCH2CONH-Tpy-ZnCl2·MeOH [complex (3)] and an octahedral nickel complex formulated as [{(MeS)3-TTF-SCH2CONH-Tpy}2Ni]·(ClO4)2·0.5(H2O) [complex (4)] are characterized in the solid state by X-ray diffraction.