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Issue 18, 2013
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Ultrafast photoinduced dynamics of halogenated cyclopentadienes: observation of geminate charge-transfer complexes in solution

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Abstract

The photoinduced dynamics of the fully halogenated cyclopentadienes C5Cl6 and C5Br6 have been investigated in solution and gas phase by femtosecond time-resolved spectroscopy. Both in solution and in gas phase, homolytic dissociation into a halogen radical and a C5X5 (X = Cl, Br) radical was observed. In liquid phase, solvent-dependent formation of charge transfer complexes between geminate radicals was observed for the first time. These complexes were found to be surprisingly stable and offered the opportunity to follow the dynamics of specific radical pairs. In the case of C5Cl6 in trichloroethanol, a reaction of the chlorine radical with molecules from the solvent cage was observed.

Graphical abstract: Ultrafast photoinduced dynamics of halogenated cyclopentadienes: observation of geminate charge-transfer complexes in solution

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Publication details

The article was received on 30 Nov 2012, accepted on 08 Feb 2013, published on 11 Feb 2013 and first published online on 11 Feb 2013


Article type: Paper
DOI: 10.1039/C3CP44295K
Citation: Phys. Chem. Chem. Phys., 2013,15, 6673-6683
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    Ultrafast photoinduced dynamics of halogenated cyclopentadienes: observation of geminate charge-transfer complexes in solution

    T. J. A. Wolf, O. Schalk, R. Radloff, G. Wu, P. Lang, A. Stolow and A.-N. Unterreiner, Phys. Chem. Chem. Phys., 2013, 15, 6673
    DOI: 10.1039/C3CP44295K

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