Australian Journal of Chemistry Australian Journal of Chemistry Society
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A Comparative Study of the Structural, Optical, and Electrochemical Properties of Squarate-Based Coordination Frameworks

Pavel M. Usov A , Tony D. Keene A B and Deanna M. D’Alessandro A C
+ Author Affiliations
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A School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.

B School of Chemistry and Physics, The University of Adelaide, Adelaide, SA 5005, Australia.

C Corresponding author. Email: deanna@chem.usyd.edu.au

Australian Journal of Chemistry 66(4) 429-435 https://doi.org/10.1071/CH12474
Submitted: 17 October 2012  Accepted: 24 November 2012   Published: 19 December 2012

Abstract

Systematic studies of the thermal expansion, optical, and redox properties of a series of six squarate-based frameworks, [MII(C4O4)(H2O)2] (MII = MnII, FeII, CoII, NiII, ZnII, CdII) have revealed that five members of the series exhibit cubic structures in which the squarate ligands are configured in an ‘eclipsed’ phase, while the CdII analogue exhibits a trigonal structure with a ‘staggered’ orientation of the ligands. The ‘eclipsed’ structures are characterised by a positive coefficient of thermal expansion, while the CdII analogue exhibits zero thermal expansion. Ultraviolet-visible-near infrared (UV-Vis-NIR) spectra and electrochemical measurements indicate that electron delocalisation across the dianionic squarate bridge is absent.


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