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Issue 6, 2016
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Assembly of inorganic [Mo2S2O2]2+ panels connected by selenite anions to nanoscale chalcogenide–polyoxometalate clusters

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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.

Graphical abstract: Assembly of inorganic [Mo2S2O2]2+ panels connected by selenite anions to nanoscale chalcogenide–polyoxometalate clusters

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Supplementary files

Article information


Submitted
23 Dec 2015
Accepted
25 Feb 2016
First published
25 Feb 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 3798-3804
Article type
Edge Article

Assembly of inorganic [Mo2S2O2]2+ panels connected by selenite anions to nanoscale chalcogenide–polyoxometalate clusters

H. Zang, J. Chen, D. Long, L. Cronin and H. N. Miras, Chem. Sci., 2016, 7, 3798
DOI: 10.1039/C5SC04944J

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