[V₁₆O₃₈(CN)]^9–: a soluble mixed-valence redox-active building block with strong antiferromagnetic coupling

Keene, Tony D., D’Alessandro, Deanna M., Krämer, Karl W., Price, Jason R., Price, David J., Decurtins, Silvio and Kepert, Cameron J. (2012) [V₁₆O₃₈(CN)]^9–: a soluble mixed-valence redox-active building block with strong antiferromagnetic coupling. Inorganic Chemistry, 51 (17), 9192-9199. (doi:10.1021/ic3001834).

Abstract

A new discrete [V₁₆O₃₈(CN)]^9- cluster, which displays the hitherto unknown 8- charge on the duster shell and is the first to encapsulate the cyanide anion, has been synthesized and characterized by IR and UV/vis/near-IR spectroscopy, electrochemistry, and magnetic susceptibility measurements. Bond valence sum calculations conducted on the basis of the crystal structure analysis of K₉[V₁₆O₃₈(CN)]·13H₂O confirm that this new member of the polyoxovanadate series is a mixed-valence complex. The intervalence charge transfer bands arising from intrametal interactions reveal that a localized (class II) assignment is appropriate for the duster; however, a small degree of electronic delocalization is present. Interesting possibilities exist for the incorporation of this unit into higher dimensionality framework structures, where the redox, optical, and magnetic properties can be exploited and tuned.

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Contributors

Author: Tony D. Keene

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