Allolio, Christoph and Stangl, Thomas and Eder, Theresa and Schmitz, Daniela and Vogelsang, Jan and Hoeger, Sigurd and Horinek, Dominik and Lupton, John M. (2018) H-Aggregation Effects between pi-Conjugated Chromophores in Cofacial Dinners and Trimers: Comparison of Theory and Single-Molecule Experiment. JOURNAL OF PHYSICAL CHEMISTRY B, 122 (24). pp. 6431-6441. ISSN 1520-6106,
Full text not available from this repository. (Request a copy)Abstract
Excited-state interchromophoric couplings in pi-conjugated polymers present a daunting challenge to study as their spectroscopic signatures are difficult to separate from structure-dependent intrachromophoric spectral characteristics. Using custom-designed molecular model systems in combination with single-molecule spectroscopy, a controlled coupling of the excited states between cofacially arranged pi-conjugated oligomers is shown to be possible. Multiscale molecular dynamics simulations allow us to generate a representative ensemble of molecular structures of the model molecule embedded in a polymer matrix and examine the connection between structural fluctuations of the molecule with theoretically predicted and measured spectral signatures. The single molecules in the embedding matrix polymer can be assigned to specific conformational features with the help of computer-based "virtual spectroscopy". By combining a quantum chemical approach with an analytical approach, we show that the coupling between the chromophores is well-described by transition dipole coupling above an interchromophoric separation of similar to 4.5 angstrom. Even for aligned chromophores, however, twisting between repeat units of the Jr-system and bending of the individual pi-systems can lead to a decoupling of the chromophores to a degree far beyond what their equilibrium structures would suggest: tiny displacements of the molecular constituents can dramatically impact excited-state interactions. This observation has profound implications for the design of future tunable organic optoelectronic materials.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | BASIS-SETS; FLUORESCENCE; EFFICIENT; POLYMERS; PHOTOPHYSICS; APPROXIMATE; SIMULATIONS; DISPERSION; PATHWAYS; EXCHANGE; |
| Subjects: | 500 Science > 530 Physics 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Physics > Institute of Experimental and Applied Physics > Chair Professor Lupton > Group John Lupton Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > Prof. Dr. Dominik Horinek |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Mar 2020 09:21 |
| Last Modified: | 09 Mar 2020 09:21 |
| URI: | https://pred.uni-regensburg.de/id/eprint/14385 |
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