Synthesis, assembly, and sizing of neutral, lanthanide substituted molybdenum blue wheels {Mo90Ln10}

Garrido Ribó, E., Bell, N. L. , Xuan, W., Luo, J., Long, D.-L. , Liu, T. and Cronin, L. (2020) Synthesis, assembly, and sizing of neutral, lanthanide substituted molybdenum blue wheels {Mo90Ln10}. Journal of the American Chemical Society, 142(41), pp. 17508-17514. (doi: 10.1021/jacs.0c07146) (PMID:32965108)

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Abstract

Polyoxometalate molybdenum blue (MB) complexes typically exist as discrete multianionic clusters and are composed of repeating Mo building units. MB wheels such as {Mo176} and {Mo154} are made from pentagon-centered {Mo8} building blocks joined by equal number of {Mo1} units as loin, and {Mo2} dimer units as skirt along the ring edge, with the ring sizes of the MB wheels modulated by the {Mo2} units. Herein we report a new class of contracted lanthanide-doped MB structures that have replaced all the {Mo2} units with lanthanide ions on the inner rim, giving the general formula {Mo90Ln10}. We show three examples of this new decameric {Mo90Ln10} (Ln = La, Ce, and Pr) framework synthesized by high temperature reduction and demonstrate that later Ln ions result in {Mo92Ln9} (Ln = Nd, Sm), conserving one {Mo2} linker unit in its structure, as a consequence of the lanthanide contraction. Remarkably the {Mo90Ln10} 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.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Xuan, Mr Weimin and Garrido Ribó, Eduard and Bell, Dr Nicola and Long, Dr Deliang and Cronin, Professor Lee
Authors: Garrido Ribó, E., Bell, N. L., Xuan, W., Luo, J., Long, D.-L., Liu, T., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:23 September 2020
Copyright Holders:Copyright © 2020 American Chemical Society
First Published:First published in Journal of the American Chemical Society 142(41): 17508-17514
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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