Macrocyclic Thiophene-Appended Cyanido-Bridged CoIII/FeII Complexes: Precursors to Mixed-valent Poly-thiophene Hybrid Materials

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doi:10.1071/CH09245

Macrocyclic Thiophene-Appended Cyanido-Bridged Co^III/Fe^II Complexes: Precursors to Mixed-valent Poly-thiophene Hybrid Materials*

Sharizal Hasan ^A, Nathan L. Kilah ^A, Manuel Martinez ^B, Paul V. Bernhardt ^A ^C

^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





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

Abstract

The new cyanido-bridged mixed valent Fe^II/Co^III macrocyclic complexes [L²Co^III(μ-NC)Fe^II(CN)₅]^– and trans-[L²Co^III(μ-NC)Fe^II(CN)₄(μ-CN)Co^IIIL²]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.

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