A novel hexadentate ligand, N-(pyridin-2-ylmethyl)-N,N′-(bis-(2-(pyridin-2-ylmethylthio))ethyethanamine) (L), containing “N 4 S 2 ” donor-set was synthesized. Its reaction with one equivalent of divalent metal perchlorate salts, M(ClO 4 ) 2 ·6H 2 O (M=Zn, Cu, and Co), in methanol yielded three mononuclear complexes [ML](ClO 4 ) 2 (M=Zn, 1; Cu, 2; Co, 3) in octahedral geometry. The complexes were fully characterized and their structures were determined using X-ray single crystal diffraction analysis. UV–Vis spectra of the complexes revealed that metal-to-ligand charge transfer (MLCT) transition bands showed readily red-shift in the trend of Zn(II), Co(II), and Cu(II) complexes. Upon the divalent metal binding, the ligand-based reduction process shifted positively which, otherwise, is not observable in the electrochemical window.