Exciton Localization in Extended pi-Electron Systems: Comparison of Linear and Cyclic Structures

Thiessen, Alexander and Wuersch, Dominik and Jester, Stefan-S. and Aggarwal, A. Vikas and Idelson, Alissa and Bange, Sebastian and Vogelsang, Jan and Hoeger, Sigurd and Lupton, John M. (2015) Exciton Localization in Extended pi-Electron Systems: Comparison of Linear and Cyclic Structures. JOURNAL OF PHYSICAL CHEMISTRY B, 119 (30). pp. 9949-9958. ISSN 1520-6106,

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Abstract

We employ five pi-conjugated mod-el 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 similar to 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 pi-conjugated system in terms of disorder parameters.

Item Type: Article
Uncontrolled Keywords: SINGLE-MOLECULE SPECTROSCOPY; CONJUGATED POLYMERS; ENERGY-TRANSFER; CONFORMATIONAL RELAXATION; TORSIONAL RELAXATION; DISORDER; FLUORESCENCE; HEXAMETHYLSEXITHIOPHENE; MACROCYCLES; EXCITATION;
Subjects: 500 Science > 530 Physics
Divisions: Physics > Institute of Experimental and Applied Physics > Chair Professor Lupton > Group John Lupton
Depositing User: Dr. Gernot Deinzer
Date Deposited: 03 Jul 2019 13:24
Last Modified: 03 Jul 2019 13:24
URI: https://pred.uni-regensburg.de/id/eprint/5173

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