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Issue 23, 2006
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Kinetically locked, trinuclear RuII metallo-macrocycles—synthesis, electrochemical, and optical properties

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Abstract

Using a [RuII([9]aneS3)] templating moiety, kinetically-locked, metallomacrocycles incorporating adenine based ligands have been synthesised through self-assembly. The kinetically robust nature of these structures is confirmed by electrochemical studies: each can be reversibly oxidised in a four-member redox series, containing two formally mixed valence states. Unusually, the electrochemically derived comproportionation constants for these mixed valence states are very different, suggesting that intermetallic coupling differs between the two states. Spectroelectochemistry studies confirm that while the [RuII2RuIII] state is valence localised, the [RuIIRuIII2] state is electronically delocalised. Mechanisms by which this switching effect could occur, which involve the unusual connectivities in these mixed valence species, are presented.

Graphical abstract: Kinetically locked, trinuclear RuII metallo-macrocycles—synthesis, electrochemical, and optical properties

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Publication details

The article was received on 11 Nov 2005, accepted on 18 Jan 2006 and first published on 04 May 2006


Article type: Paper
DOI: 10.1039/B516080B
Dalton Trans., 2006, 2900-2906

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    Kinetically locked, trinuclear RuII metallo-macrocycles—synthesis, electrochemical, and optical properties

    N. Shan, J. D. Ingram, T. L. Easun, S. J. Vickers, H. Adams, M. D. Ward and J. A. Thomas, Dalton Trans., 2006, 2900
    DOI: 10.1039/B516080B

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