56099 20200221144333.0 doi 10.1039/c5nj02773j sideral 93688 ART-2016-93688 eng Lang, Z. On the formation of gold nanoparticles from [AuIIICl4]- and a non-classical reduced polyoxomolybdate as an electron source: A quantum mechanical modelling and experimental study 2016 Access copy available to the general public Unrestricted Polyoxometalate (POM)-mediated reduction and nucleation mechanisms in nanoparticle (NP) syntheses are still largely unknown. We carried out comprehensive theoretical analysis using density functional theory (DFT) to gain insight into the molecular and electronic changes that occur during the reduction of HAuIIICl4 with the Kabanos-type polyoxomolybdate, Na{(MoV2O4)3(µ2-O)3(µ2-SO3)3(µ6-SO3)}2]15-. In the system presented herein the electrons are supplied by the POM, making the computational thermodynamic analysis more feasible. Our results reveal that this particular POM is a multi-electron source and the proton-coupled electron transfer (PCET) greatly promotes the reduction process. Based on the energy and molecular orbital studies of the intermediate species the reduction of AuIII to AuI is shown to be thermodynamically favourable, and a low HOMO-LUMO gap of the POM-Au superstructure is advantageous for electron transfer. By modelling the reduction of three couples of AuIII ¿ AuI by the same POM unit, it is proposed that the reduced polyoxomolybdate is finally fully oxidised. The subjacent idea of using the Kabanos POM was confirmed by comprehensive experimental characterisation of POM-stabilised gold nanoparticles (AuNPs@POM). Present theoretical analysis suggests that protons have a significant influence on the final AuI to Au0 reduction step that ultimately leads to colloidal AuNPs@POM. info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-29054 info:eu-repo/grantAgreement/EC/FP7/239931/EU/Multifunctional Magnetic Nanoparticles: Towards Smart Drugs Design/NANOPUZZLE info:eu-repo/semantics/openAccess by-nc http://creativecommons.org/licenses/by-nc/3.0/es/ 3.269 2016 CHEMISTRY, MULTIDISCIPLINARY 52 / 166 = 0.313 2016 Q2 T1 0.868 2016 Chemistry (miscellaneous) 2016 Q1 Materials Chemistry 2016 Q1 Catalysis 2016 Q2 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Maicas Gabas, I. López, X. Clotet, A. (orcid)0000-0003-1081-8482 Martínez de la Fuente, J. Universidad de Zaragoza Mitchell, S.G. Poblet, J.M. 2013 765 Universidad de Zaragoza Dpto. Química Orgánica Área Química Orgánica 40, 2 (2016), 1029-1038 New j. chem. NEW JOURNAL OF CHEMISTRY 1144-0546 2687577 http://zaguan.unizar.es/record/56099/files/texto_completo.pdf Versión publicada 112697 http://zaguan.unizar.es/record/56099/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:56099 articulos driver 2020-02-21-13:46:22 ARTICLE