Ribó, E. G., Bell, N. L. , Long, D.-l. and Cronin, L. (2022) Engineering highly reduced molybdenum polyoxometalates via the incorporation of d and f block metal ions. Angewandte Chemie (International Edition), 61(21), e202201672. (doi: 10.1002/anie.202201672) (PMID:35257462)
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Abstract
The assembly of nanoscale polyoxometalate (POM) clusters has been dominated by the highly reduced icosahedral {Mo 132 } ‘browns’ and the toroidal {Mo 154 } ‘blues’ which are 45% and 18% reduced respectively. We hypothesised that there is space for a greater diversity of structures in this immediate reduction zone. Here we show it is possible to make highly reduced mix-valence POMs by presenting new classes of polyoxomolybdates: [Mo V 52 Mo VI 12 H 26 O 200 ] 42- {Mo 64 } and [Mo V 40 Mo VI 30 H 30 O 215 ] 20- {Mo 70 }. The {Mo 64 } cluster archetype has a super-cube structure and is composed of five different types of building blocks, each arranged in overlayed Archimedean or Platonic polyhedra. The {Mo 70 } cluster comprises five tripodal {Mo V 6 } and five tetrahedral {Mo V 2 Mo VI 2 } building blocks alternatively linked to form a loop with a pentagonal star topology. We also show how the reaction yielding the {Mo 64 } super-cube can be used in the enrichment of lanthanides which exploit the differences in selectivity in the self-assembly of the polyoxometalates.
| Item Type: | Articles |
|---|---|
| Additional Information: | This work was supported the EPSRC grants (No. EP/J015156/1; EP/L023652/1; EP/I033459/1; EP/K023004/1; and EP/L023652/1); the European Research Council (project 670467 SMART-POM); and the University of Glasgow. |
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Long, Dr Deliang and Bell, Dr Nicola and Cronin, Professor Lee |
| Authors: | Ribó, E. G., Bell, N. L., Long, D.-l., and Cronin, L. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Angewandte Chemie (International Edition) |
| Publisher: | Wiley |
| ISSN: | 1433-7851 |
| ISSN (Online): | 1521-3773 |
| Published Online: | 07 March 2022 |
| Copyright Holders: | Copyright © 2022 The Authors |
| First Published: | First published in Angewandte Chemie (International Edition) 61(21): e202201672 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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