Probing the self-assembly of inorganic cluster architectures in solution with cryospray mass spectrometry: Growth of polyoxomolybdate clusters and polymers mediated by silver(I) ions

Wilson, E. F., Abbas, H., Duncombe, B. J., Streb, C., Long, D. L. and Cronin, L. (2008) Probing the self-assembly of inorganic cluster architectures in solution with cryospray mass spectrometry: Growth of polyoxomolybdate clusters and polymers mediated by silver(I) ions. Journal of the American Chemical Society, 130(42), pp. 13876-13884. (doi:10.1021/ja802514q)

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Abstract

Cryospray mass spectrometry (CSI-MS) has been used to probe the mechanism of self-assembly of polyoxometalate clusters in solution. By using CSI-MS and electronic absorbance spectroscopy it was possible to monitor in real-time the self-assembly of polymeric chains based on [Ag2Mo8O26](2-)(n) building blocks. The role of the Ag-I ion in the solution state rearrangement of molybdenum Lindqvist ({Mo-6}) into the silver-linked beta-octamolybdate ({Mo-8}) structure ((n-C4H9)(4)N)(2n)[Ag2Mo8O26](n) (1) is revealed in unprecedented detail. A monoanionic series, in particular [AgMomO3m+1](-) where m = 2 to 4, and series involving mixed oxidation state polyoxomolybdate species, which illustrate the in-solution formation of the (Ag{Mo-8}Ag) building blocks, have been observed. CSI-MS detection of species with increasing metal nuclearity concomitant with increasing organic cation contribution supports the hypothesis that the organic cations used in the synthesis play an important structure-directing role in polyoxometalate (POM) growth in solution. A real-time decrease in [{Mo-6}] and associated increase in [{Mo-8}] have been observed using CSI-MS and electronic absorbance spectroscopy, and the rate Of {Mo-6} interconversion to ({Mo-8}) was found to decrease on increasing the size of the countercation. This result can be attributed to the steric bulk of larger organic groups hindering {Mo-6} to {Mo-6} rearrangement and hindering the contact between silver cations and molybdenum anions.

Item Type:Articles
Keywords:ANION ANIONS ARCHITECTURES BUILDING-BLOCKS CATION CATIONS CHAIN CLUSTER CLUSTERS DAWSON DERIVATIVES GROWTH ION IONS mass spectrometry MASS-SPECTROMETRY MECHANISM MOLYBDATE Molybdenum OXIDATION PHYSICAL-PROPERTIES POLYMERS POLYOXOMETALATE POLYOXOMETALATE CLUSTERS POLYOXOMOLYBDATE REACTION-KINETICS rearrangement SELF-ASSEMBLIES self-assembly silver SPECTROSCOPY STATE Structure SYMMETRY
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Long, Dr Deliang and Cronin, Professor Lee and Streb, Mr Carsten
Authors: Wilson, E. F., Abbas, H., Duncombe, B. J., Streb, C., Long, D. L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
ISSN:0002-7863

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