Synthesis and characterisation of novel ruthenium multi-substituted polyoxometalates: alpha,beta-[SiW9O37Ru4(H2O)(3)Cl-3](7-)

abstract

Novel ruthenium multi-substituted polyoxometalate compounds of general formulae K6Na[SiW9O37Ru4III(H2O)(3)Cl-3]center dot nH(2)O (alpha- and beta-SiW9O34 isomers) were synthesised via the reactions of the trilacunary Keggin alpha- and beta-[SiW9O34](10-) anions with RuCl3 in aqueous solution. Characterisation was performed by analytical, spectroscopic, magnetic, and electrochemical techniques. The results are in accordance with the new polyoxometalates having the trivacant Keggin anion (alpha or beta isomer) linked to a cubane-type Ru4O4 cluster. The co-ordination sphere of ruthenium is completed with water molecules and chloride anions. Magnetic measurements showed that the majority of the molecules have the Ru ions cluster in a compensated configuration constrained to an antiferromagnetic alignment at very low temperature and following a Curie-Weiss like behaviour. For both isomers, cyclic voltammetry revealed quasi-reversible redox processes at the ruthenium centres, namely Ru-IV/III and Ru-III/II, which were found to be pH dependent. The novel polyoxotungstates incorporate the highest content of ruthenium (W:Ru = 2.25:1) ever reported for Keggin-, Dawson or sandwich-type transition metal-substituted polyoxometalates and may find promising applications as oxidative catalysts. (C) 2010 Elsevier Ltd. All rights reserved.

keywords

KEGGIN-TYPE POLYOXOTUNGSTATES; SUBSTITUTED POLYOXOMETALATE; STRUCTURAL-CHARACTERIZATION; ELECTROCHEMICAL-BEHAVIOR; HYDROTHERMAL SYNTHESIS; CATALYTIC CHEMISTRY; MAGNETIC-PROPERTIES; ALKENE OXIDATION; MOLECULAR-OXYGEN; WATER OXIDATION

subject category

Chemistry; Crystallography

authors

Gamelas, JAF; Carapuca, HM; Balula, MS; Evtuguin, DV; Schlindwein, W; Figueiras, FG; Amaral, VS; Cavaleiro, AMV

our authors

acknowledgements

Authors wish to thank the University of Aveiro and the Portuguese Foundation for the Science and Technology (FCT) for funding. The authors also thank Dr. N.J.O. Silva for additional magnetic measurements performed at Zaragoza University, Spain and Dr. C.P. Moreira de Sa CEMUP Porto-Portugal, for XPS analysis. J.A.F. Gamelas thanks FCT for the award of a postdoctoral research grant (SFRH/BPD/11571/2002).

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