On the Spin-State Dependence of Redox Potentials of Spin Crossover Complexes

Inorg Chem. 2020 Dec 21;59(24):18402-18406. doi: 10.1021/acs.inorgchem.0c03043. Epub 2020 Dec 7.

Abstract

Resistance switching properties of nanoscale junctions of spin crossover molecules have received recently much interest. In many cases, this property has been traced back to the variation of molecular orbital energies upon spin transition. However, one can also expect a substantial reorganization of the molecular structure due to charge localization, which calls for a better understanding of the relationship between the redox potential and the spin state of the molecule. To investigate this issue, we carried out a detailed density functional theory and variable temperature cyclic voltammetry investigation of the benchmark compound [Fe(HB(1,2,4-triazol-1-yl)3)2] in solution. We show that, for a correct thermodynamical picture, it is necessary to take into account the charge transfer-induced electronic and structural reorganization as well as spin equilibria in the oxidized and reduced species.