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Inorganics 2015, 3(2), 279-294; doi:10.3390/inorganics3020279

Fully Oxidized and Mixed-Valent Polyoxomolybdates Structured by Bisphosphonates with Pendant Pyridine Groups: Synthesis, Structure and Photochromic Properties

1
Institut Lavoisier de Versailles, UMR8180, Université de Versailles St Quentin en Yvelines, 45 Avenue des Etats Unis, 78035 Versailles cedex, France
2
Institut des Matériaux Jean-Rouxel, Université de Nantes, CNRS, 2 Rue de la Houssinière, BP 32229, 44322 Nantes cedex, France
These authors contributed equally to this work.
*
Authors to whom correspondence should be addressed.
Academic Editors: Greta Ricarda Patzke and Pierre-Emmanuel Car
Received: 16 April 2015 / Accepted: 29 May 2015 / Published: 11 June 2015
(This article belongs to the Special Issue Polyoxometalates)
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Abstract

Hybrid organic-inorganic polyoxometalates (POMs) were synthesized in water by the reaction of a MoVI precursor with bisphosphonate ligands functionalized by pyridine groups. The fully oxidized POM [(MoVI3O8)2(O)(O3PC(O)(C3H6NH2CH2C5H4NH)PO3)2]4− has been isolated as water insoluble pure Na salt (NaMo6(Ale-4Py)2) or mixed Na/K salt (NaKMo6(Ale-4Py)2) and their structure solved using single-crystal X-ray diffraction. The mixed-valent complex [(MoV2O4)(MoVI2O6)2{O3PC(O)(C3H6N(CH2C5H4N)2(MoVIO3))PO3}2]8− was obtained as an ammonium salt (NH4Mo6(AlePy2Mo)2), in the presence of a reducing agent (hydrazine). 31P NMR spectroscopic studies in aqueous media have allowed determining the pH stability domain of NH4Mo6(AlePy2Mo)2. NaMo6(Ale-4Py)2 and NaKMo6(Ale-4Py)2 exhibit remarkable solid-state photochromic properties in ambient conditions. Under UV excitation, they develop a very fast color-change from white to deep purple and proved to be the fastest photochromic organoammonium/POM systems. The coloration kinetics has been fully quantified for both salts and is discussed in light of the hydrogen-bonding networks. View Full-Text
Keywords: bisphosphonate; hydrogen bonds; molybdenum; photochromism; polyoxometalate bisphosphonate; hydrogen bonds; molybdenum; photochromism; polyoxometalate
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MDPI and ACS Style

Oms, O.; Benali, T.; Marrot, J.; Mialane, P.; Puget, M.; Serier-Brault, H.; Deniard, P.; Dessapt, R.; Dolbecq, A. Fully Oxidized and Mixed-Valent Polyoxomolybdates Structured by Bisphosphonates with Pendant Pyridine Groups: Synthesis, Structure and Photochromic Properties. Inorganics 2015, 3, 279-294.

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