Crystal Structures, Magnetic Properties, and Redox Behaviors of Carboxylato-Bridged Mn(II) Complexes with Ditopic Ligands Featuring N3-Coordination Sites

Carboxylato-bridged dinuclear and tetranuclear Mn(II) complexes 1-3 with ditopic ligands featuring two N-3-terminal coordination sites connected by hexyl (tphn), octyl (tpon), and p-xylyl (tpxn) linkers have been synthesized and characterized through X-ray single-crystal structure analyses, infrared spectroscopy, and elemental analyses. Complex 1 is a mu-fluorido-bis-mu-acetato dinuclear Mn(II) complex where the ligand tphn coordinates to both terminal sides of a dinuclear Mn unit. In contrast, complexes 2 and 3 are tetranuclear Mn(II) complexes with a macrocyclic structure, in which two dinuclear Mn units are linked by ligands tpon or tpxn. The redox behaviors of 1 and 2 were elucidated by cyclic voltammetry, revealing two metal-centered redox processes corresponding to Mn-2(II,II)/Mn-2(II,III) and Mn-2(II,III)/Mn-2(III,III).