Medina Rivero, Samara;
Alonso-Navarro, Matías J;
Tonnelé, Claire;
Marín-Beloqui, Jose M;
Suárez-Blas, Fátima;
Clarke, Tracey M;
Kang, Seongsoo;
... Casado, Juan; + view all
(2023)
V-Shaped Tröger Oligothiophenes Boost Triplet Formation by CT Mediation and Symmetry Breaking.
Journal of the American Chemical Society
, 145
(50)
pp. 27295-27306.
10.1021/jacs.3c06916.
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Abstract
A new family of molecules obtained by coupling Tröger’s base unit with dicyanovinylene-terminated oligothiophenes of different lengths has been synthesized and characterized by steady-state stationary and transient time-resolved spectroscopies. Quantum chemical calculations allow us to interpret and recognize the properties of the stationary excited states as well as the time-dependent mechanisms of singlet-to-triplet coupling. The presence of the diazocine unit in Tröger’s base derivatives is key to efficiently producing singlet-to-triplet intersystem crossing mediated by the role of the nitrogen atoms and of the almost orthogonal disposition of the two thiophene arms. Spin–orbit coupling-mediated interstate intersystem crossing (ISC) is activated by a symmetry-breaking process in the first singlet excited state with partial charge transfer character. This mechanism is a characteristic of these molecular triads since the independent dicyanovinylene-oligothiophene branches do not display appreciable ISC. These results show how Tröger’s base coupling of organic chromophores can be used to improve the ISC efficiency and tune their photophysics.
| Type: | Article |
|---|---|
| Title: | V-Shaped Tröger Oligothiophenes Boost Triplet Formation by CT Mediation and Symmetry Breaking |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/jacs.3c06916 |
| Publisher version: | http://dx.doi.org/10.1021/jacs.3c06916 |
| Language: | English |
| Additional information: | Copyright © 2023 American Chemical Society. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/) . |
| Keywords: | Excited States, Molecules, Nitrogen, Oligomers, Thiophenes |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10183900 |
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