Engineering highly reduced molybdenum polyoxometalates via the incorporation of d and f block metal ions

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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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
166449Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1Chemistry
190796Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1Chemistry
166779Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1Chemistry
166449Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1Chemistry
167864Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1Chemistry
190796Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1Chemistry
172151SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467Chemistry