V-Shaped Troger Oligothiophenes Boost Triplet Formation by CT Mediation and Symmetry Breakingopen access
- Authors
- Rivero, Samara Medina; Alonso-Navarro, Matias J.; Tonnele, Claire; Marin-Beloqui, Jose M.; Suarez-Blas, Fatima; Clarke, Tracey M.; Kang, Seongsoo; Oh, Juwon; Ramos, M. Mar; Kim, Dongho; Casanova, David; Segura, Jose L.; Casado, Juan
- Issue Date
- Dec-2023
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.145, no.50, pp 27295 - 27306
- Pages
- 12
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Volume
- 145
- Number
- 50
- Start Page
- 27295
- End Page
- 27306
- URI
- https://scholarworks.bwise.kr/sch/handle/2021.sw.sch/26719
- DOI
- 10.1021/jacs.3c06916
- ISSN
- 0002-7863
1520-5126
- Abstract
- A new family of molecules obtained by coupling Tro''ger'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 Tro''ger'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 Tro''ger's base coupling of organic chromophores can be used to improve the ISC efficiency and tune their photophysics.
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