Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
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Macrocyclic Thiophene-Appended Cyanido-Bridged CoIII/FeII Complexes: Precursors to Mixed-valent Poly-thiophene Hybrid Materials*

Sharizal Hasan A , Nathan L. Kilah A , Manuel Martinez B and Paul V. Bernhardt A C
+ Author Affiliations
- Author Affiliations

A School of Chemistry and Molecular Biosciences University of Queensland, Brisbane, Qld 4072, Australia.

B Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, E-08028 Barcelona, Spain.

C Corresponding author. Email: p.bernhardt@uq.edu.au

Australian Journal of Chemistry 62(10) 1214-1220 https://doi.org/10.1071/CH09245
Submitted: 25 April 2009  Accepted: 25 June 2009   Published: 13 October 2009

Abstract

The new cyanido-bridged mixed valent FeII/CoIII macrocyclic complexes [L2CoIII(μ-NC)FeII(CN)5] and trans-[L2CoIII(μ-NC)FeII(CN)4(μ-CN)CoIIIL2]2+ have been prepared and characterized spectroscopically. The trinuclear complex trans-[L2Co(μ-NC)Fe(CN)4(μ-CN)CoL2](ClO4)2·11H2O has been characterized crystallographically. The di- and trinuclear complexes exhibit metal-to-metal charge transfer transitions characteristic of Class II mixed valent chromophores and their redox and spectroscopic properties have been analyzed by Hush theory. The thiophene group attached to the macrocycle L2 in these complexes may serve as a precursor to conducting polythiophene-based hybrid materials incorporating redox active transition metal ions.


Acknowledgement

S.H. gratefully acknowledges a UiTM Malaysia PhD scholarship provided by the Malaysian Government. P.V.B. acknowledges financial support from the Australian Research Council. M.M. acknowledges DGI grant CTQ2006–14909-C02–02.


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* In memory of Professor Alan M. Sargeson; an inspirational leader in Australian chemistry.


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