Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand

Abstract

A new redox-active hydrazone ligand bearing a phenalenol group is described (phpl), which produces neutral six-coordinate Fe and Co complexes (1 & 2) with the ligands identified in different oxidation states; an open-shell anion radical and closed-shell dianion. An intense and very low-energy intervalence charge transfer (IVCT) band is identified in solid-state and in solution in the complexes. Single crystals of 1 are semiconducting (at 300 K, σ = 3.05 × 10⁻⁴ S cm⁻¹ with E_a = 245 meV).