Metal-Dependent and Redox-Selective Coordination Behaviors of Metalloligand [MoV(1,2-benzenedithiolato)3]− with CuI/AgI Ions

The synthesis and characterization of two coordination polymers, {CuI[MoV(bdt)3]·0.5Et2O}n (1·0.5Et2O, bdt: o-benzenedithiolato) and {AgI[MoV(bdt)3]}n (2), composed of redox-active [MoV(bdt)3]− metalloligand with CuI and AgI ions are reported. The complexation reactions of [MoV(bdt)3]− with CuII(ClO4)2 or AgIClO4 commonly lead to the formation of one-dimensional (1-D) coordination polymers. The presence of CuI in 1·0.5Et2O strongly indicates that the CuII ion is reduced during the complexation reaction with [MoV(bdt)3]−, which acts as an electron donor. The total dimensionalities of the assembled structures of 1·0.5Et2O and 2 are significantly different and related to the type of additional metal ions, CuI and AgI. In contrast to the isolated 1-D chain structure of 1·0.5Et2O, complex 2 has a three-dimensional (3-D) assembled structure constructed from additional π−π stacking interactions between adjacent [MoV(bdt)3]− moieties. These structural differences influence the solubility of the complexes in organic solvents; complex 1·0.5Et2O is soluble as origomeric species in highly polar solvents, while 2 is insoluble in organic solvents and water. Coordination polymers 1·0.5Et2O and 2 were investigated by UV−vis spectroscopy in the solid state, and that in solution together with their electrochemical properties were also investigated for 1 because of its higher solubility in polar organic solvents. Complex 1·0.5Et2O dissolved in CH3CN demonstrates concentration-dependent UV−vis spectra supporting the presence of coordinative interactions between [MoV(bdt)3]− moieties and CuI ions to create the origomeric species even in solutions, an observation that is supported also by electrochemical experiments.