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Issue 38, 2011
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Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

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Abstract

This article discusses recent progress by a combination of spectroscopy and quantum-chemical calculations in classifying and characterizing organic mixed-valence systems in terms of their localized vs. delocalized character. A recently developed quantum-chemical protocol based on non-standard hybrid functionals and continuum solvent models is evaluated for an extended set of mixed-valence bis-triarylamine radical cations, augmented by unsymmetrical neutral triarylamine-perchlorotriphenylmethyl radicals. It turns out that the protocol is able to provide a successful assignment to class II or class III Robin-Day behavior and gives quite accurate ground- and excited-state properties for the radical cations. The limits of the protocol are probed by the anthracene-bridged system 8, where it is suspected that specific solute–solvent interactions are important and not covered by the continuum solvent model. Intervalence charge-transfer excitation energies for the neutral unsymmetrical radicals are systematically overestimated, but dipole moments and a number of other properties are obtained accurately by the protocol.

Graphical abstract: Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

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Publication details

The article was received on 01 Jun 2011, accepted on 03 Aug 2011 and first published on 31 Aug 2011


Article type: Perspective
DOI: 10.1039/C1CP21772K
Phys. Chem. Chem. Phys., 2011,13, 16973-16986

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    Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?

    M. Kaupp, M. Renz, M. Parthey, M. Stolte, F. Würthner and C. Lambert, Phys. Chem. Chem. Phys., 2011, 13, 16973
    DOI: 10.1039/C1CP21772K

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