Temporal Fluctuations in Excimer-Like Interactions between π-Conjugated Chromophores.

Autor:	Stangl T; †Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany., Wilhelm P; †Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany., Schmitz D; ‡Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany., Remmerssen K; ‡Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany., Henzel S; ‡Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany., Jester SS; ‡Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany., Höger S; ‡Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany., Vogelsang J; †Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany., Lupton JM; †Institut für Experimentelle und Angewandte Physik, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany.
Jazyk:	angličtina
Zdroj:	The journal of physical chemistry letters [J Phys Chem Lett] 2015 Apr 16; Vol. 6 (8), pp. 1321-6. Date of Electronic Publication: 2015 Mar 27.
DOI:	10.1021/acs.jpclett.5b00328
Abstrakt:	Inter- or intramolecular coupling processes between chromophores such as excimer formation or H- and J-aggregation are crucial to describing the photophysics of closely packed films of conjugated polymers. Such coupling is highly distance dependent and should be sensitive to both fluctuations in the spacing between chromophores as well as the actual position on the chromophore where the exciton localizes. Single-molecule spectroscopy reveals these intrinsic fluctuations in well-defined bichromophoric model systems of cofacial oligomers. Signatures of interchromophoric interactions in the excited state--spectral red shifting and broadening and a slowing of photoluminescence decay--correlate with each other but scatter strongly between single molecules, implying an extraordinary distribution in coupling strengths. Furthermore, these excimer-like spectral fingerprints vary with time, revealing intrinsic dynamics in the coupling strength within one single dimer molecule, which constitutes the starting point for describing a molecular solid. Such spectral sensitivity to sub-Ångström molecular dynamics could prove complementary to conventional FRET-based molecular rulers.
Databáze:	MEDLINE
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