A solvent- and temperature-dependent intramolecular equilibrium of diamagnetic and paramagnetic states in Co complexes bearing triaryl amines

Dalton Trans. 2018 Oct 7;47(37):13180-13189. doi: 10.1039/c8dt02538j. Epub 2018 Sep 4.

Abstract

Complexes [Co(L)2](ClO4)2 (L = o-substituted 2-(pyridine-2-yl)-1,10-phenanthrolines 1a-c) containing three redox active centres (a Co2+ ion and two triaryl amine (Tara) units) have been synthesised. The order of oxidation steps in [Co(L)2](ClO4)2 (L = 1a-c) was determined using cyclic voltammetry and EPR/UV-vis-NIR spectroelectrochemistry. In acetonitrile solutions, at room temperature, the first oxidation is Co-centred followed by the Tara oxidation at more anodic potentials. The order of oxidation is inverted in solutions of the less polar solvent dichloromethane. The Co3+/2+-centred redox event leads to a spin transition between the paramagnetic high-spin (HS) Co2+ and the diamagnetic low-spin (LS) Co3+ state, which was proven using 1H NMR and EPR spectroscopy. After one-electron oxidation of [Co(L)2](ClO4)2, an equilibrium between the diamagnetic [Co3+(L)]3+ and paramagnetic [Co2+(L)(L+)]3+ state in [Co(L)2]3+ (L = 1a-c) was found. Cyclic voltammetry showed enhanced intermolecular electron transfer between the [Co2+(L)2]2+ and [Co3+(L)2]3+ redox states mediated by [Co2+(L)(L+)]3+. Variable temperature vis-NIR spectroscopy of in situ generated [Co(L)2]3+ revealed a temperature-dependent redox equilibrium between the [Co3+(L)2]3+ and the [Co2+(L+)(L)]3+ states (L = 1a-c). Magnetic coupling between the HS-Co2+ ion and the Tara+ radical in [HS-Co2+(L+)(L)]3+ (L = 1a,c) was deduced from broad and undetectable lines observed in the corresponding EPR spectra. Complete oxidation to [LS-Co3+(L+)2]5+ (L = 1a,c) leads to characteristic EPR spectra of Tara biradicals with non-interacting spins.