Issue 8, 2005
From the journal:

Dalton Transactions

Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeII complexes

Brendan P. Macpherson,†*a   Basam M. Alzoubi,b   Paul V. Bernhardt,a   Manuel Martínez,c   Peter A. Tregloan*d  and  Rudi van Eldik‡*b  

* Corresponding authors

a Department of Chemistry, The University of Queensland, Brisbane, Australia

b Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstr. 1, Erlangen, Germany

c Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, Barcelona, Spain

d School of Chemistry, The University of Melbourne, Parkville, Australia

Abstract

The effects of pressure and temperature on the energy (Eop) of the metal-to-metal charge transfer (MMCT, FeII→CoIII) transition of the cyano-bridged complexes trans-[L14CoNCFe(CN)5]− and cis-[L14CoNCFe(CN)5]− (where L14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) were examined. The changes in the redox potentials of the cobalt and iron metal centres with pressure and temperature were also examined and the results interpreted with Marcus–Hush theory. The observed redox reaction volumes can mainly be accounted for in terms of localised electrostriction effects. The shifts in Eop due to both pressure and temperature were found to be less than the shifts in the energy difference (ΔE°) between the CoIII–FeII and CoII–FeIII redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of CoII, are discussed in order to account for this trend. To study the effect of pressure on CoIII electronic absorption bands, a new cyano-bridged complex, trans-[L14CoNCCo(CN)5], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans-[L14CoNCFe(CN)5]·5H2O.

Graphical abstract: Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeII complexes

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Article information

DOI
https://doi.org/10.1039/B418054B
Article type
Paper
Submitted
30 Nov 2004
Accepted
22 Feb 2005
First published
17 Mar 2005

Dalton Trans., 2005, 1459-1467

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Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged CoIII–FeII complexes

B. P. Macpherson, B. M. Alzoubi, P. V. Bernhardt, M. Martínez, P. A. Tregloan and R. van Eldik, Dalton Trans., 2005, 1459 DOI: 10.1039/B418054B

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