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Issue 13, 2014
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Assembly and core transformation properties of two tetrahedral clusters: [FeIII13P8W60O227(OH)15(H2O)2]30− and [FeIII13P8W60O224(OH)12(PO4)4]33−

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Abstract

Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII13P8W60O227(OH)15(H2O)2]30− (1) and [FeIII13P8W60O224(OH)12(PO4)4]33− (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [α-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 {FeIII13} 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 {Fe13} core to a {K⊂Fe12} 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.

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

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Publication details

The article was received on 01 Dec 2013, accepted on 29 Jan 2014 and first published on 11 Feb 2014


Article type: Paper
DOI: 10.1039/C3DT53382D
Citation: Dalton Trans., 2014,43, 5190-5199
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    Assembly and core transformation properties of two tetrahedral clusters: [FeIII13P8W60O227(OH)15(H2O)2]30− and [FeIII13P8W60O224(OH)12(PO4)4]33−

    P. I. Molina, H. N. Miras, D. Long and L. Cronin, Dalton Trans., 2014, 43, 5190
    DOI: 10.1039/C3DT53382D

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