Hydrazone-based cobalt complexes toward multielectron redox and spin crossover

Abstract

Hydrazone-based derivatives modified by substitution at different positions were utilized to prepare a series of bis-homoleptic cobalt complexes. One species, [Co^III(L1)₂]⁺ (1), which incorporated deprotonated ligands, adopted a Co(III) diamagnetic ground state. However, the substituent of a hydrogen atom with a methyl group precluded the possibility of deprotonation upon metal coordination, which led to two species, [Co^II(L2^Me)₂]²⁺ (2) and [Co^II(L3^NO2)₂]²⁺, (3) which underwent a gradual spin crossover with an adjustable substituent effect and a mixed character of low-spin (doublet) and high-spin (quartet) populations in wide temperature ranges. Depending on the electronic effects of the substituents on the ligand, the multielectron redox behavior of the cobalt center was systematically modulated as well. This result demonstrates redox-switchable spin crossover in a new hydrazone-based Co(II) system, in which the deprotonation of the coordination pocket and substituent groups in aromatic ligands can have a profound effect on the redox potential and spin state of the metal center.