Synthesis, Assembly and Sizing of Neutral, Lanthanide Substituted Molybdenum Blue Wheels {Mo 90+2n Ln 10-n }.

Polyoxometalate molybdenum blue (MB) complexes typically exist as discrete multianionic clusters and are composed of repeating Mo building units. MB wheels such as {Mo-176} and {Mo-154} are made from pentagon-centered {Mo-8} building blocks joined by equal number of {Mo-1} units as loin, and {Mo-2} dimer units as skirt along the ring edge, with the ring sizes of the MB wheels modulated by the {Mo-2} units. Herein we report a new class of contracted lanthanide-doped MB structures that have replaced all the {Mo-2} units with lanthanide ions on the inner rim, giving the general formula {Mo(90)Ln(10)}. We show three examples of this new decameric {Mo(90)Ln(10)} (Ln = La, Ce, and Pr) framework synthesized by high temperature reduction and demonstrate that later Ln ions result in {Mo(92)Ln(9)} (Ln = Nd, Sm), conserving one {Mo-2} linker unit in its structure, as a consequence of the lanthanide contraction. Remarkably the {Mo(90)Ln(10)} compounds are the first examples of charge-neutral molybdate wheels as confirmed by BVS, solubility experiments, and redox titrations. We detail our full synthetic optimization for the isolation of these clusters and complete characterization by X-ray, TGA, UV-vis, and ICP studies. Finally, we show that this fine-tuned self-assembly process can be utilized to selectively enrich Ln-MB wheels for effective separation of lanthanides.