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Title

Rates of Electronic Energy Transfer in Conformationally Flexible Bichromophoric Macrocyclic Complexes: A Combined Experimental and Molecular Modeling Study

Authors
Moore, Evan G.
Bernhardt, Paul V.
Riley, Mark J.
Published in Journal of Physical Chemistry. A. 2003, vol. 107, no. 41, p. 8396-8403
Abstract Electronic energy transfer (EET) rate constants between a naphthalene donor and anthracene acceptor in [ZnL4a](ClO4)2 and [ZnL4b](ClO4)2 were determined by time-resolved fluorescence where L4a and L4b are the trans and cis isomers of 6-((anthracen-9-yl-methyl)amino)-6,13-dimethyl-13-((naphthalen-1-yl-methyl)amino)-1,4,8,11-tetraazacyclotetradecane, respectively. These isomers differ in the relative disposition of the appended chromophores with respect to the macrocyclic plane. The trans isomer has an energy transfer rate constant (kEET) of 8.7 × 10(8) s-1, whereas that of the cis isomer is significantly faster (2.3 × 10(9) s-1). Molecular modeling was used to determine the likely distribution of conformations in CH3CN solution for these complexes in an attempt to identify any distance or orientation dependency that may account for the differing rate constants observed. The calculated conformational distributions together with analysis by 1H NMR for the [ZnL4a]2+ trans complex in the common trans-III N-based isomer gave a calculated Förster rate constant close to that observed experimentally. For the [ZnL4b]2+ cis complex, the experimentally determined rate constant may be attributed to a combination of trans-III and trans-I N-based isomeric forms of the complex in solution.
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Research group Groupe Vauthey
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MOORE, Evan G. et al. Rates of Electronic Energy Transfer in Conformationally Flexible Bichromophoric Macrocyclic Complexes: A Combined Experimental and Molecular Modeling Study. In: Journal of Physical Chemistry. A, 2003, vol. 107, n° 41, p. 8396-8403. https://archive-ouverte.unige.ch/unige:3509

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Deposited on : 2009-10-02

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