Description:
<jats:title>Abstract</jats:title><jats:p>The synthesis, spectroscopic, electrochemical, magnetic, and structural characterization of the dinuclear series of complexes [(MOM<jats:sub>2</jats:sub>tom<jats:sup>Me</jats:sup>){<jats:italic>M</jats:italic><jats:sup>II</jats:sup>Cl<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>] (<jats:italic>M</jats:italic><jats:sup>II</jats:sup> = Zn<jats:sup>II</jats:sup>, Cu<jats:sup>II</jats:sup>, Ni<jats:sup>II</jats:sup>, Co<jats:sup>II</jats:sup>, Fe<jats:sup>II</jats:sup>) and, for comparison, the structure of the complex [(MOM<jats:sub>2</jats:sub>tom){Zn<jats:sup>II</jats:sup>Cl<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>] are presented. The metal ions are five‐coordinate in N<jats:sub>3</jats:sub>Cl<jats:sub>2</jats:sub> environments. The coordination polyhedra are evaluated in the solid‐state by single‐crystal X‐ray crystallography and in solution by UV/Vis/NIR spectroscopy for the Cu<jats:sup>II</jats:sup> and Fe<jats:sup>II</jats:sup> complexes. All complexes exhibit a ligand‐centered irreversible oxidation in the range 1.17–1.40 V vs. Fc<jats:sup>+</jats:sup>/Fc, whereas the complexes with Fe<jats:sup>II</jats:sup>, Co<jats:sup>II</jats:sup>, and Ni<jats:sup>II</jats:sup> exhibit additional reversible metal‐centered oxidations of 0.09, 0.70, and 0.87 V vs. Fc<jats:sup>+</jats:sup>/Fc, respectively. The coordination of the chloride ligands saturates the Lewis‐acidity of the metal ions so that the MOM groups are not cleaved. Bands at 1161 and 1020 cm<jats:sup>–1</jats:sup> in the FT‐IR spectra are a signature for the presence of the MOM groups. Reaction with copper(II) acetate at room temperature results in the complex [(MOM<jats:sub>2</jats:sub>tom<jats:sup>Me</jats:sup>){Cu<jats:sup>II</jats:sup>(OAc)<jats:sub>2</jats:sub>}<jats:sub>2</jats:sub>] while the reaction at 50 °C for several hours resulted in the simultaneous MOM cleavage and complexation and thus isolation of [(tom<jats:sup>Me</jats:sup>){Cu(OAc)}<jats:sub>2</jats:sub>]. This successful synthetic route will be applied to establish a series of [(tom<jats:sup>Me</jats:sup>){<jats:italic>M</jats:italic>(OAc)}<jats:sub>2</jats:sub>] with different metal ions in order to compare their DNA binding ability and cytotoxicity to cancer cells to that of the copper(II) complex.</jats:p>