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• W2027899529 startingPage "5101" @default.
• W2027899529 abstract "The synthesis and structural characterization of the neutral mixed-valence methoxo-polyoxovanadium cluster [V6O8(OCH3)11] (1) and its single oxidation product in the hexachloroantimonate salt [V6O8(OCH3)11][SbCl6] (2) are presented here. The cluster comprises a hexauclear polyoxovanadate core of the Lindqvist structure, of which all but one of the μ-bridging oxo ligands are substituted by methoxo. As revealed by cyclic voltammetry, the cluster is highly redox active, displaying several further thermodynamically stable VIV/VV mixed-valence redox derivatives. Furthermore, valence sum calculations performed on the X-ray structural data as well as results from IR and UV−vis spectrometry characterize them as class II mixed-valence compounds. In the present article, we equally present results from cyclic voltammetry, UV−vis spectrometry, and magnetic measurements obtained for members of the previously reported [V6O7(OCH3)12] cluster series, which, as opposed to 1 and its derivatives, contain exclusively methoxo ligands as μ-bridging moieties. Magnetic measurements performed on the highly reduced cluster species [VIV5VV1O7(OCH3)12]− and [VIV6O7(OCH3)12]2− reveal net antiferromagnetic exchange interactions between the d-electrons, which at lower temperatures are in part suppressed for reasons attributed to geometric spin frustration. Among the present results, the comparison of the cyclic voltammograms of 1 and [V6O7(OCH3)12] has proven to be of considerable interest, showing an unexpectedly pronounced discrepancy in all but one of their corresponding redox potentials. In particular, a detailed analysis of the electrochemical conversions indicates that the observed shift is almost entirely the result of a different degree of d-electron spin−spin interactions in corresponding mixed valence species of the cluster series." @default.
• W2027899529 created "2016-06-24" @default.
• W2027899529 creator A5017031448 @default.
• W2027899529 creator A5084390541 @default.
• W2027899529 date "2009-03-20" @default.
• W2027899529 modified "2023-09-29" @default.
• W2027899529 title "A Mixed-Valence V^IV/V^V Alkoxo-polyoxovanadium Cluster Series [V₆O₈(OCH₃)₁₁]^{<i>n</i>+/−}: Exploring the Influence of a μ-Oxo Ligand in a Spin Frustrated Structure" @default.
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• W2027899529 doi "https://doi.org/10.1021/ja8073648" @default.
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