A Dinuclear Cobalt Complex Featuring Unprecedented Anodic and Cathodic Redox Switches for Single-Molecule Magnet Activity

摘要

One-electron oxidation or reduction of the paramagnetic dinuclearCo(II) complex dmp2Nin{Co[N(SiMe3)2]}2 (1; dmp2Nin2− = bis(2,6-dimethylphenyl)nindigo), by fully reversible chemical or electrochemical methods,generates the radical salts [1(OEt2)]+ and [1]−, respectively. Full structural andmagnetic analyses reveal the locus of the redox changes to be nindigo-based, thus givingrise to ligand-centered radicals sandwiched between two paramagnetic and lowcoordinateCo(II) centers. The presence of these sandwiched radicals mediatesmagnetic coupling between the high-spin (S = 3/2) cobalt ions, which gives rise tosingle-molecule magnet (SMM) activity in both the oxidized ([1(OEt2)]+) and reduced([1]−) states. This feature represents the first example of a SMM exhibiting fullyreversible, dual “ON/OFF” switchability in both the cathodic and anodic states.