Configurable nanosized metal oxide oligomers via precise “click” coupling control of hybrid polyoxometalates

MacDonell, A., JOHNSON, N. A.B., Surman, A. J. and Cronin, L. (2015) Configurable nanosized metal oxide oligomers via precise “click” coupling control of hybrid polyoxometalates. Journal of the American Chemical Society, 137(17), pp. 5662-5665. (doi:10.1021/jacs.5b02466) (PMID:25846763)

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Abstract

Polyoxometalates (POMs) are discrete clusters of redox-active metal oxides, many of which can be linked to organic moieties. Here, we show how it is possible to link Mn Anderson POMs to terminal alkyne and azide groups and develop appropriate conditions for their Cu-catalyzed alkyne–azide cycloaddition (or “click” reaction). These coupling reactions are then used to link the clusters together, forming monodisperse linear Mn Anderson oligomers, here with examples ranging in size from two to five clusters. These oligomers are built up sequentially using a combination of mono- and difunctionalized clusters, giving an unprecedented level of control over the size and structure of the resulting hybrid POMs. This new synthetic methodology therefore opens the way for the synthesis of metal oxide hybrid oligomers and polymers by coupling control, minimizing side products, producing nanosized molecular hybrid organic–inorganic oxides ca. 4–9 nm in size, with molecular weights ranging 2–10 kDa.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:JOHNSON, Naomi and Cronin, Professor Lee and Surman, Dr Andrew and MacDonell, Mr Andrew
Authors: MacDonell, A., JOHNSON, N. A.B., Surman, A. J., 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

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY