Issue 16, 2011
From the journal:

Physical Chemistry Chemical Physics

Exploring the thermochromism of sulfite-embedded polyoxometalate capsules†

Ryo Tsunashima,a   De-Liang Long,a   Toru Endo,b   Shin-ichiro Noro,bc   Tomoyuki Akutagawa,bc   Takayoshi Nakamura,bc   Raul Quesada Cabrera,d   Paul F. McMillan,d   Paul Kögerlere  and  Leroy Cronin*a  

* Corresponding authors

a WestCHEM, Department of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, UK
E-mail: l.cronin@chem.gla.ac.uk
Fax: +44 (0)141 330 4888

b Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0810, Japan

c Research Institute for Electronic Science, Hokkaido University, Sapporo 001-0020, Japan

d Department of Chemistry and Materials Chemistry Centre, Christopher Ingold Laboratories, University College London, London WC1H 0AJ, UK

e Institut für Anorganische Chemie, RWTH Aachen University, 52074 Aachen, Germany

Abstract

The Dawson-type polyanion [α-Mo18O54(SO3)2]4−, with two SO32− templates embedded inside a polyoxomolybdate(VI) cage, exhibits thermochromism over an exceptionally wide temperature range (∼500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO–LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion.

Graphical abstract: Exploring the thermochromism of sulfite-embedded polyoxometalate capsules

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Article information

DOI
https://doi.org/10.1039/C1CP20074G
Article type
Communication
Submitted
09 Jan 2011
Accepted
17 Feb 2011
First published
15 Mar 2011

Phys. Chem. Chem. Phys., 2011,13, 7295-7297

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Exploring the thermochromism of sulfite-embedded polyoxometalate capsules

R. Tsunashima, D. Long, T. Endo, S. Noro, T. Akutagawa, T. Nakamura, R. Q. Cabrera, P. F. McMillan, P. Kögerler and L. Cronin, Phys. Chem. Chem. Phys., 2011, 13, 7295 DOI: 10.1039/C1CP20074G

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