Magnetic on-off switching in redox non-innocent ligand bridged binuclear cobalt complexes

摘要

The redox non-innocent ligand 2,2-bipyrimidine (bpym) reacted with two molar equivalents of LCo(tol) (L = CH(MeC?NAr)(2), Ar = 2,6-iPr(2)C(6)H(3)) to afford the binuclear Co-II complex (LCo)(2)(-bpym) (1), in which the bpym moiety accepts two electrons from the metal centers and in the dianion state. Complex 1 readily underwent one-electron oxidation when treated with [Cp2Fe](+)[BPh4](-) affording the cation salt [(LCo)(2)(-bpym)][BPh4] (2) with the bpym moiety in the radical anion state. Meanwhile, complex 2 could be converted back to 1 with elemental potassium. The magnetic studies revealed that complex 2 is a single molecular magnet (SMM) under a small external field, while 1 has no SMM activity. This represents a new example of a SMM exhibiting a fully reversible on/off' switching ability in anodic and neutral states.