Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer

A series of hetero-bimetallic transition metal-substituted polyoxometalates (TMSPs) were synthesized based on the CoII-centered ligand [CoIIW11O39]10–. The eight complex series, [CoII(MxOHy)W11O39](12–x−y)– (MxOHy = VIVO, CrIII(OH2), MnII(OH2), FeIII(OH2), CoII(OH2), NiII(OH2), CuII(OH2), ZnII(OH2)), of which six are reported for the first time, was synthesized starting from [CoIIIW11O39]9– and studied using spectroscopic, electrochemical, and computational techniques to evaluate the influence of substituted transition metals on the photodynamics of the metal-to-polyoxometalate charge transfer (MPCT) transition. The bimetallic complexes all show higher visible light absorption than the plenary [CoIIW12O40]6– and demonstrate the same MPCT transition as the plenary complex, but they have shorter excited-state lifetimes (sub-300 ps in aqueous media). The decreased lifetimes are rationalized on the basis of nonradiative relaxation due to coordinating aqua ligands, increased interaction with cations due to inc...