title: Exciton Localization in Extended π-Electron Systems: Comparison of Linear and Cyclic Structures.
abstract: We employ five π-conjugated model materials of different molecular shape-oligomers and cyclic structures-to investigate the extent of exciton self-trapping and torsional motion of the molecular framework following optical excitation. Our studies combine steady state and transient fluorescence spectroscopy in the ensemble with measurements of polarization anisotropy on single molecules, supported by Monte Carlo simulations. The dimer exhibits a significant spectral red shift within ∼100 ps after photoexcitation which is attributed to torsional relaxation. This relaxation mechanism is inhibited in the structurally rigid macrocyclic analogue. However, both systems show a high degree of exciton localization but with very different consequences: while, in the macrocycle, the exciton localizes randomly on different parts of the ring, scrambling polarization memory, in the dimer, localization leads to a deterministic exciton position with luminescence characteristics of a dipole. Monte Carlo simulations allow us to quantify the structural difference between the emitting and absorbing units of the π-conjugated system in terms of disorder parameters.
authors.affiliation: †Department of Physics and Astronomy, University of Utah, Salt Lake City, Utah 84112, United States.
authors.forename: Alexander
authors.initials: A
authors.lastname: Thiessen
authors.affiliation: ‡Institut für Experimentelle und Angewandte Physik, Universität Regensburg, 93040 Regensburg, Germany.
authors.forename: Dominik
authors.initials: D
authors.lastname: Würsch
authors.affiliation: §Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, 53121 Bonn, Germany.
authors.forename: Stefan-S
authors.initials: SS
authors.lastname: Jester
authors.affiliation: §Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, 53121 Bonn, Germany.
authors.forename: A Vikas
authors.initials: AV
authors.lastname: Aggarwal
authors.affiliation: §Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, 53121 Bonn, Germany.
authors.forename: Alissa
authors.initials: A
authors.lastname: Idelson
authors.affiliation: ‡Institut für Experimentelle und Angewandte Physik, Universität Regensburg, 93040 Regensburg, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Bange
authors.affiliation: ‡Institut für Experimentelle und Angewandte Physik, Universität Regensburg, 93040 Regensburg, Germany.
authors.forename: Jan
authors.initials: J
authors.lastname: Vogelsang
authors.affiliation: §Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, 53121 Bonn, Germany.
authors.forename: Sigurd
authors.initials: S
authors.lastname: Höger
authors.affiliation: †Department of Physics and Astronomy, University of Utah, Salt Lake City, Utah 84112, United States.|‡Institut für Experimentelle und Angewandte Physik, Universität Regensburg, 93040 Regensburg, Germany.
authors.forename: John M
authors.initials: JM
authors.lastname: Lupton