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Issue 45, 2011
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Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters

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Abstract

A complimentary combination of Density Functional Theory (DFT) methodology and Electrospray Ionization-Mass Spectrometry (ESI-MS) has been utilized to increase our limited understanding of the first nucleation steps in the formation of the [XM12O40]n Keggin polyoxometalates (POMs) (where addenda metal atom M = W or Mo, and the heteroatom X = P or As). We postulate that the first key steps of nucleation into discrete, high nuclearity heteropolyanions proceed via the formation of isodinuclear species (e.g.[M2O7]2), which undergo successive steps of protonation and water condensation to form a heterotrinuclear fragment, which acts as a template for the constituent parts required for subsequent aggregation and formation of the plenary Keggin heteropolyanion. The stability of calculated structures of the numerous postulated intermediates has been analysed and discussed in detail, and these results complemented using experimental mass spectrometry, using an assembly (reaction solution analysis) and disassembly (fragmentation of single crystals) approach. Overall, no significant differences between the Keggin POMs were found when changing the addenda metal atom (W or Mo) or the heteroatom (P or As); although small differences among the lowest-energy structures were detected.

Graphical abstract: Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters

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Publication details

The article was received on 16 Apr 2011, accepted on 26 Jul 2011 and first published on 24 Aug 2011


Article type: Paper
DOI: 10.1039/C1CP21209E
Citation: Phys. Chem. Chem. Phys., 2011,13, 20136-20145
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    Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters

    L. Vilà-Nadal, S. G. Mitchell, A. Rodríguez-Fortea, H. N. Miras, L. Cronin and J. M. Poblet, Phys. Chem. Chem. Phys., 2011, 13, 20136
    DOI: 10.1039/C1CP21209E

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