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Issue 18, 2013

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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Submitted
30 Nov 2012
Accepted
08 Feb 2013
First published
11 Feb 2013

Phys. Chem. Chem. Phys., 2013,15, 6673-6683
Article type
Paper

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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