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Issue 5, 2010
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Estimation of the solvent reorganization energy and the absolute energy of solvation of charge-transfer states from their emission spectra

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Abstract

We report herein the solvent and temperature effects on the emission of the intermolecular exciplexes 1-cyanonaphthalene/triethylamine and 1-methylnaphthalene/triethylamine and the intramolecular exciplexes formed by the bichromophoric compounds diethyl-(3-naphthalen-1-yl-propyl)-amine (I), diethyl-(2-naphthalen-1-yl-ethyl)-amine (II), 3-[ethyl-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (III) and 3-[(2-cyano-ethyl)-(2-naphthalen-1-yl-ethyl)-amino]-propionitrile (IV). The results are interpreted within the formalism of the semiclassical Marcus theory for radiative back electron transfer (BET) reactions. We show that, following a few simple assumptions, reliable values of the Gibbs free energy changes (ΔGεet) and the solvent reorganization energies (λεs) associated to the BET reactions (and their corresponding enthalpic and entropic contributions) can be estimated directly from the emission of the CT states. We also show that for the 1-cyanonaphthalene/triethylamine exciplex, which exhibits emission in the vapour phase, the experimental calculation of the absolute energy of solvation of the CT state (ΔGεs) is also possible. The calculated ΔGεet correlate quite satisfactorily with the corresponding values obtained from independent electrochemical and kinetics experiments. The temperature effects on ΔGεet, λεs and ΔGεs are discussed qualitatively using different solvation models. The limitations of the present approach for the estimation of ΔGεet and λεs and its possible application to more complex A/D systems are also examined.

Graphical abstract: Estimation of the solvent reorganization energy and the absolute energy of solvation of charge-transfer states from their emission spectra

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Publication details

The article was received on 07 Dec 2009, accepted on 04 Feb 2010 and first published on 10 Mar 2010


Article type: Paper
DOI: 10.1039/B9PP00190E
Citation: Photochem. Photobiol. Sci., 2010,9, 675-686
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    Estimation of the solvent reorganization energy and the absolute energy of solvation of charge-transfer states from their emission spectra

    C. Solís, V. Grosso, N. Faggioli, G. Cosa, M. Romero, C. Previtali, H. Montejano and C. Chesta, Photochem. Photobiol. Sci., 2010, 9, 675
    DOI: 10.1039/B9PP00190E

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