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Inorganics 2016, 4(2), 14; doi:10.3390/inorganics4020014

Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates

1
Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, Spain
2
BCMaterials, Parque Científico y Tecnológico de Bizkaia, Derio 48160, Spain
3
Servicios Generales de Investigación SGIker, Universidad del País Vasco UPV/EHU, Bilbao 48080, Spain
4
Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, Spain
5
Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, Spain
*
Authors to whom correspondence should be addressed.
Academic Editors: Greta Ricarda Patzke and Lee J. Higham
Received: 31 March 2016 / Revised: 27 April 2016 / Accepted: 3 May 2016 / Published: 12 May 2016
(This article belongs to the Special Issue Organophosphorus Chemistry 2016)
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Abstract

New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates. View Full-Text
Keywords: polyoxometalates; organophosphonates; charge transfer; fluorescence; solution stability polyoxometalates; organophosphonates; charge transfer; fluorescence; solution stability
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MDPI and ACS Style

Andino, N.; Artetxe, B.; Reinoso, S.; Vitoria, P.; San Felices, L.; Martínez, J.I.; López Arbeloa, F.; Gutiérrez-Zorrilla, J.M. Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates. Inorganics 2016, 4, 14.

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