Tuning the metal-to-metal charge transfer energy of cyano-bridged dinuclear complexes

Bernhardt, Paul V., Bozoglian, Fernando, Macpherson, Brendan P. and Martinez, Manuel (2004) Tuning the metal-to-metal charge transfer energy of cyano-bridged dinuclear complexes. Dalton Transactions, 16: 2582-2587. doi:10.1039/b407185a

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Author Bernhardt, Paul V.
Bozoglian, Fernando
Macpherson, Brendan P.
Martinez, Manuel
Title Tuning the metal-to-metal charge transfer energy of cyano-bridged dinuclear complexes
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
Publication date 2004
Sub-type Article (original research)
DOI 10.1039/b407185a
Open Access Status File (Publisher version)
Issue 16
Start page 2582
End page 2587
Total pages 6
Place of publication Cambridge
Publisher Royal Society of Chemistry
Collection year 2004
Language eng
Subject C1
250201 Transition Metal Chemistry
780103 Chemical sciences
Abstract The metal-to-metal charge transfer (MMCT) transitions of a series of Class II mixed valence dinuclear complexes bearing cyano bridging ligands may be varied systematically by variations to either the hexacyanometallate(II) donor or Co-III acceptor moieties. Specifically, the new dinuclear species trans-[(LCoNCFe)-Co-14S(CN)(5)](-) (L-14S = 6-methyl-1,11-diaza-4,8-dithia- cyclotetradecane-6-amine) and trans-[(LCoNCRu)-Co-14(CN)(5)]-(L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine) have been prepared and their spectroscopic and electrochemical properties are compared with the relative trans-[(LCoNCFe)-Co-14(CN)(5)](-). The crystal structures of Na{trans-[(LCoNCFe)-Co-14S(CN)(5)]}.51/2H(2)O.1/2EtOH, Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.3H(2)O and Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.8H(2)O are also reported. The ensuing changes to the MMCT energy have been examined within the framework of Hush theory, and it was found that the free energy change between the redox isomers was the dominant effect in altering the energy of the MMCT transition.
Keyword Chemistry, Inorganic & Nuclear
Amino-substituted Tetraazacycloalkanes
Quinquedentate Coordination
Cobalt(iii) Complexes
Q-Index Code C1

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Created: Wed, 15 Aug 2007, 04:04:24 EST