Assembly and core transformation properties of two tetrahedral clusters:([FeIII13P8W60O227(OH)15(H2O)2]30− and [FeIII13P8W60O224(OH)12(PO4)4]33−

Molina, P. I., Miras, H. N. , Long, D.-L. and Cronin, L. (2014) Assembly and core transformation properties of two tetrahedral clusters:([FeIII13P8W60O227(OH)15(H2O)2]30− and [FeIII13P8W60O224(OH)12(PO4)4]33−. Dalton Transactions, 43(13), pp. 5190-5199. (doi:10.1039/c3dt53382d)

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Abstract

Two nanosized 2.6 nm Fe-III substituted polyoxotungstates (Fe13P8W60O227)-P-III(OH)(15)(H2O)(2)(30-) (1) and Fe-13(III) P8W60O224(OH)(12)(PO4)(4)(33-) (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor alpha-P2W15O56(12-) and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An Fe-13(III) core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K+-triggered transformation of the Fe-13 core to a KCFe12 core in solution. Cyclic voltammetry shows the presence of independent W-and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr Deliang and Molina-Sanchez, Mr Pedro and Moiras, Dr Haralampos and Cronin, Professor Lee
Authors: Molina, P. I., Miras, H. N., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Dalton Transactions
Publisher:Royal Society of Chemistry
ISSN:1477-9226
ISSN (Online):1477-9234

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