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

Sharizal Hasan; Nathan L. Kilah; Manuel Martinez; Paul V. Bernhardt

doi:10.1071/CH09245

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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 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 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.

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.

References

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

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

Abstract

Acknowledgement

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