Controlling the self-assembly of a mixed-metal Mo/V-selenite family of polyoxometalates

Corella-Ochoa, M.N., Miras, N., Long, D.L. and Cronin, L. (2012) Controlling the self-assembly of a mixed-metal Mo/V-selenite family of polyoxometalates. Chemistry: A European Journal, 18(43), pp. 13743-13754. (doi: 10.1002/chem.201200912)

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Five mixed-metal mixed-valence Mo/V polyoxoanions, templated by the pyramidal SeO32- heteroanion have been isolated: K10MoVI12VV10O58(SeO3)8]center dot 18?H2O (1), K7MoVI11VV5VIV2O52(SeO3)]center dot 31?H2O (2), (NH4)7K3MoVI11VV5VIV2O52(SeO3)(MoV6VV- O22)]center dot 40?H2O (3), (NH4)19K3MoVI20VV12VIV4O99(SeO3)10]center dot 36?H2O (4) and Na3(H2O)5{Mo18-xVxO52(SeO3)} {Mo9-yVyO24(SeO3)4}] (5). All five compounds were characterised by single-crystal X-ray structure analysis, TGA, UV/Vis and FT-IR spectroscopy, redox titrations, and elemental and flame atomic absorption spectroscopy (FAAS) analysis. X-ray studies revealed two novel coordination modes for the selenite anion in compounds 1 and 4 showing eta,mu and mu,mu coordination motifs. Compounds 1 and 2 were characterised in solution by using high-resolution ESI-MS. The ESI-MS spectra of these compounds revealed characteristic patterns showing distribution envelopes corresponding to 2- and 3- anionic charge states. Also, the isolation of these compounds shows that it may be possible to direct the self-assembly process of the mixed-metal systems by controlling the interplay between the cation shrink-wrapping effect, the non-conventional geometry of the selenite anion and fine adjustment of the experimental variables. Also a detailed IR spectroscopic analysis unveiled a simple way to identify the type of coordination mode of the selenite anions present in POM-based architectures.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Moiras, Dr Haralampos and Long, Dr Deliang and Cronin, Professor Lee
Authors: Corella-Ochoa, M.N., Miras, N., Long, D.L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Journal Abbr.:Chem. Eur J.
ISSN (Online):1521-3765
Published Online:20 September 2012

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