Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes

Macpherson, Brendan P., Alzoubi, Basam M., Bernhardt, Paul V., Martinez, Manuel, Tregloan, Peter A. and van Eldik, Rudi (2005) Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes. Dalton Transactions, 8: 1459-1467. doi:10.1039/b418054b

Attached Files (Some files may be inaccessible until you login with your UQ eSpace credentials)
Name Description MIMEType Size Downloads
UQ76142_OA.pdf Full text (open access) application/pdf 272.98KB 0

Author Macpherson, Brendan P.
Alzoubi, Basam M.
Bernhardt, Paul V.
Martinez, Manuel
Tregloan, Peter A.
van Eldik, Rudi
Title Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes
Formatted title
Pressure and temperature effects on metal-to-metal charge transfer in cyano-bridged Co-III-Fe-II complexes
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
1477-9234
Publication date 2005-04-21
Sub-type Article (original research)
DOI 10.1039/b418054b
Open Access Status File (Publisher version)
Issue 8
Start page 1459
End page 1467
Total pages 9
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Collection year 2005
Language eng
Subject 250201 Transition Metal Chemistry
780103 Chemical sciences
Abstract The effects of pressure and temperature on the energy (E-op) of the metal-to-metal charge transfer (MMCT, Fe-II --> Co-III) transition of the cyano-bridged complexes trans - [(LCoNCFe)-Co-14(CN)(5)](-) and cis-[(LCoNCFe)-Co-14(CN)(5)](-) (where L-14 = 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 E-op due to both pressure and temperature were found to be less than the shifts in the energy difference (E degrees) between the Co-III-Fe-II and Co-II-Fe-III redox isomers. The pressure and temperature dependence of the reorganisational energy, as well as contributions arising from the different spin states of Co-II, are discussed in order to account for this trend. To study the effect of pressure on Co-III electronic absorption bands, a new cyano-bridged complex, trans - [(LCoNCCo)-Co-14(CN)(5)], was prepared and characterised spectroscopically and structurally. X-Ray crystallography revealed this complex to be isostructural with trans -[(LCoNCFe)-Co-14(CN)(5)] center dot 5H(2)O.
Keyword Chemistry, Inorganic & Nuclear
Cyclic Staircase Voltammetry
Electron-transfer Reactions
Redox Reaction Volumes
Solvent Reorganization
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

 
Versions
Version Filter Type
Citation counts: TR Web of Science Citation Count  Cited 18 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 16 times in Scopus Article | Citations
Google Scholar Search Google Scholar
Created: Wed, 15 Aug 2007, 06:17:30 EST