Zang, H.-Y., Chen, J.-J., Long, D. L. , Cronin, L. and Miras, H. N. (2016) Assembly of inorganic [Mo2S2O2]2+ panels connected by selenite anions to nanoscale chalcogenide–polyoxometalate clusters. Chemical Science, 7(6), pp. 3798-3804. (doi: 10.1039/c5sc04944j)
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Abstract
We describe how supramolecular assembly, mediated by control of the ratio of the hetero-atoms in the units [Mo2S2O2]2+ and SeO32− leads to the formation of new types of building blocks, [(Mo2O2S2)3(OH)4(H2O)6(SeO3)] = {Mo6} and [(Mo2O2S2)2(OH)2(H2O)4(SeO3)] = {Mo4} which are linked in an type of inorganic ‘panelling’ to the assembly of a range of new clusters 1–3 with the general formula {(Mo2O2S2)x(OH)y(SeO3)z(H2O)w}n−, where x, y, z, w, n = [8, 0, 20, 8, 24] for 1, [14, 14, 17, 8, 20] for 2 and [8, 8, 8, 0, 8] for 3. Cluster 1, a rare example of inorganic cryptand, exhibits an elliptical “endo” motif defining an anisotropic ellipse with the dimensions 1.7 × 1.0 nm, with pores ranging from 5.3 to 6.4 Å and site selective cation recognition properties; cluster 2 exhibits an “exo” structural motif constructed by 3 × {Mo6} and 2 × {Mo4} panels spanning a cross shape 2.4 × 2.0 nm and cluster 3 a ring shaped structure of a 1.5 nm in diameter. The control of endo vs. exo topology as a function of the Se:Mo ratio is reflected to the difference in surface area of ca. 500 Å2 between clusters 1 and 2 intermolecular interactions and proton conduction properties, and this work shows that very simple synthetic parameters can critically change the structure and properties of all-inorganic nanoscale chalcogenide–polyoxometalates.
| Item Type: | Articles |
|---|---|
| Status: | Published |
| Refereed: | Yes |
| Glasgow Author(s) Enlighten ID: | Moiras, Professor Haralampos and Long, Dr Deliang and Cronin, Professor Lee |
| Authors: | Zang, H.-Y., Chen, J.-J., Long, D. L., Cronin, L., and Miras, H. N. |
| College/School: | College of Science and Engineering > School of Chemistry |
| Journal Name: | Chemical Science |
| Journal Abbr.: | Chem. Sci. |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 2041-6520 |
| ISSN (Online): | 2041-6539 |
| Published Online: | 25 February 2016 |
| Copyright Holders: | Copyright © 2016 Royal Society of Chemistry |
| First Published: | First published in Chemical Science 7(6):3798-3804 |
| Publisher Policy: | Reproduced under a Creative Commons License |
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