Journal article
Electronic structure and surface properties of the mixed-valence doughnut shaped polyoxomolybdate nanocapsule Mo57V6
INORGANICA CHIMICA ACTA, Vol.363(15), pp.4368-4373
12/10/2010
DOI: 10.1016/j.ica.2010.07.019
Abstract
We report a detailed analysis of the electronic structure and results of molecular dynamics simulations for the large polyoxomolybdate [H3Mo57V6(NO)(6)O-183(H2O)(18)](21) (Mo57V6) which is a highly symmetric anion with a complex electronic structure and exhibiting a unique variety of multifunctionality. The six vanadium centres are reduced with one electron each, the six Mo centres are bonded to non-innocent NO ligands and the additional six 4d electrons are mostly delocalised over the rest of molybdenum atoms. DFT calculations carried out with the solvent - modelled by a continuum approach - suggest that despite the large charge of the anion, the Mo57V6 framework can be easily reduced in polar solvents. Furthermore, the Mo57V6 cluster has 18 water molecules trapped in its internal cavity. Molecular dynamics simulations carried out with different solvent conditions suggest that the water molecules inside the cavity have a high ordered structure over a wide range of temperatures and give important information about the cluster anion interactions with the cations present in solution. The obtained results allow a better understanding of related properties of the giant ball-shaped polyoxometalates/Keplerates as the present cluster contains similar building blocks - like the (metal)(6)O-6 type pores with crown ether-like structure. (C) 2010 Elsevier B.V. All rights reserved.
Details
- Title: Subtitle
- Electronic structure and surface properties of the mixed-valence doughnut shaped polyoxomolybdate nanocapsule Mo57V6
- Creators
- Jorge A. Fernandez - Universidad Rovira i VirgiliPere Miro - Institut Català d'Investigació QuímicaJosep Bonet-Avalos - Universidad Rovira i VirgiliCarles Bo - Institut Català d'Investigació QuímicaJosep M. Poblet - Universidad Rovira i Virgili
- Resource Type
- Journal article
- Publication Details
- INORGANICA CHIMICA ACTA, Vol.363(15), pp.4368-4373
- Publisher
- Elsevier
- DOI
- 10.1016/j.ica.2010.07.019
- ISSN
- 0020-1693
- eISSN
- 1873-3255
- Number of pages
- 6
- Grant note
- 2009FIC00026 / Autonomous Government of Catalonia; Generalitat de Catalunya 2009SGR462; 2009SGR259 / DGR of the Autonomous Government of Catalonia DGR of the Autonomous Government of Catalonia (ICIQ Foundation) European Social Fund; European Social Fund (ESF) CSD2006-0003 / Consolider Ingenio 2010 program; Ministry of Science and Innovation, Spain (MICINN); Spanish Government University and Enterprise Department of Catalan Government University and Research Commission of Innovation CTQ2008-06549/BQU / Spanish MEC; Spanish Government
- Language
- English
- Date published
- 12/10/2010
- Academic Unit
- Chemistry
- Record Identifier
- 9984618648402771
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