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

作者：Fortier Skye; Le Roy Jennifer J; Chen Chun Hsing; Vieru Veacheslav; Murugesu Muralee^*; Chibotaru Liviu F; Mindiola Daniel J; Caulton Kenneth G

来源：Journal of the American Chemical Society, 2013, 135(39): 14670-14678.

DOI：10.1021/ja405284t

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

• 出版日期2013-10-2