Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism

Winter, R.S., Yan, J., Busche, C., Mathieson, J.S., Prescimone, A., Brechin, E.K., Long, D.L. and Cronin, L. (2013) Nanoscale control of polyoxometalate assembly: a {Mn8W4} cluster within a {W36Si4Mn10} cluster showing a new type of isomerism. Chemistry: A European Journal, 19(9), pp. 2976-2981. (doi:10.1002/chem.201204345)

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Abstract

Two near isomeric clusters containing a novel {Mn8W4} Keggin cluster within a [W36Mn10Si4O136(OH)4(H2O)8]24− cluster are reported: K10Li14 [W36Si4O136MnII10(OH)4(H2O)8] (1) and K10Li13.5Mn0.25[W36Si4O136MnII10(OH)4(H2O)8] (1′). Bulk characterization of the clusters has been carried out by single crystal X-ray structure analysis, ICP-MS, TGA, ESI-MS, CV and SQUID-magnetometer analysis. X-ray analysis revealed that 1′ has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two “intermediate” types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X-ray analysis and revealed to be novel clusters K4Li22[W36Si4Mn7O136(H2O)8]⋅56 H2O (2) and Mn2K8Li14[W36Si4Mn7O136(H2O)8]⋅45 H2O (3). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X-ray crystallography directly facilitated understanding the means by which a POM assembled.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Busche, Dr Christoph and Yan, Mr Jun and Mathieson, Dr Jennifer and Long, Dr De Liang and Cronin, Professor Leroy
Authors: Winter, R.S., Yan, J., Busche, C., Mathieson, J.S., Prescimone, A., Brechin, E.K., Long, D.L., and Cronin, L.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Journal Abbr.:Chem. Eur J.
ISSN:0947-6539
ISSN (Online):1521-3765

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