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

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:Long, Dr De Liang and Moiras, Dr Charalampos and Cronin, Professor Leroy
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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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
646611Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/L023652/1CHEM - CHEMISTRY
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503295Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular LimitLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/H024107/1CHEM - CHEMISTRY
616021Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/K023004/1CHEM - CHEMISTRY
605821The Multi-Corder: Poly-Sensor TechnologyDavid CummingEngineering & Physical Sciences Research Council (EPSRC)EP/K021966/1ENG - ENGINEERING ELECTRONICS & NANO ENG
562821Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/I033459/1CHEM - CHEMISTRY
577391Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering & Physical Sciences Research Council (EPSRC)EP/J015156/1CHEM - CHEMISTRY
599451Microscale Chemically Reactive Electronic AgentsLeroy CroninEuropean Commission (EC)FP7 ICT MICRE31CHEM - CHEMISTRY