Inducing molecular growth in an {Mo57Fe6}-type nanocluster: synthesis, structure, and properties of {Mo57}(Mo)2Fe6III}

Fielden, J., Malaestean, Y.L., Ellern, A., García-Serres, R., Cronin, L. and Kögerler, P. (2006) Inducing molecular growth in an {Mo57Fe6}-type nanocluster: synthesis, structure, and properties of {Mo57}(Mo)2Fe6III}. Journal of Cluster Science, 17(2), pp. 291-302. (doi:10.1007/s10876-006-0053-1)

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Publisher's URL: http://dx.doi.org/10.1007/s10876-006-0053-1

Abstract

The reaction of the polyoxomolybdate anion [Mo<sub>32</sub><sup>IV</sup>(MoNO)<sub>4</sub>O<sub>108</sub>(H<sub>2</sub>O)<sub>16</sub>]<sup>12-</sup>with Fe<sup>II</sup> salts and hydrazine sulfate yields the cluster anion [Mo<sub>51</sub><sup>V/VI</sup>(Mo<sup>VI</sup>O)<sub>2</sub>Fe<sub>6</sub><sup>III</sup>(MoNO)<sub>6</sub>O<sub>176</sub>(OH)<sub>3</sub>(H<sub>2</sub>O)<sub>22</sub>]<sup>15-</sup> (1a), isolated as its corresponding ammonium salt (NH<sub>4</sub>)<sub>15</sub> <b>1a</b> 36H<sub>2</sub>O (<b>1</b>) (space group P63/mmc, a=b=23.607(5) Å, c=26.767(6) Å, 4076 unique reflections, 293 parameters). Despite the absence of oxygen and the reducing conditions the product comprises only Fe<sup>III</sup> centers as determined by a combination of spectroscopic, magnetic and crystallographic analysis. Reduction of peripheral Mo centers causes the aggregation of two additional [Mo<sup>VI</sup>O]<sup>4+</sup> groups onto the archetypal {Mo<sub>57</sub>M<sub>6</sub>} structure. The single-crystal X-ray determined structure of <b>1</b> is reported.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Fielden, Dr John and Cronin, Professor Lee
Authors: Fielden, J., Malaestean, Y.L., Ellern, A., García-Serres, R., Cronin, L., and Kögerler, P.
Subjects:Q Science > QD Chemistry
College/School:College of Science and Engineering > School of Chemistry
University Centres > Glasgow Materials Research Initiative
Journal Name:Journal of Cluster Science
Publisher:Kluwer Academic Publishers-Plenum Publishers
ISSN:1040-7278
ISSN (Online):1572-8862

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