RT Journal Article
T1 V-Shaped tröger oligothiophenes boost triplet formation by CT mediation and symmetry breaking
A1 Medina Rivero, Samara
A1 Alonso-Navarro, Matías J.
A1 Tonnelé, Claire
A1 Marín-Beloqui, Jose M.
A1 Suárez-Blas, Fátima
A1 Clarke, Tracey M.
A1 Kang, Seongsoo
A1 Oh, Juwon
A1 Ramos, Mar
A1 Kim, Dongho
A1 Casanova, David
A1 Segura Castedo, José Luis
A1 Casado, Juan
AB 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 timeresolved spectroscopies. Quantum chemical calculations allow us to interpret and recognize the properties of the stationary excited states as well as the timedependent mechanisms of singlet-to-triplet coupling. The presence of the diazocine unit in Tröger’s base derivatives is key to efficiently producing singletto-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 displayappreciable ISC. These results show how Tröger’s base coupling of organic chromophores can be used to improve the ISC efficiency and tune their photophysics.
SN 0002-7863
SN 1520-5126
YR 2023
FD 2023
LK https://hdl.handle.net/20.500.14352/102813
UL https://hdl.handle.net/20.500.14352/102813
LA eng
NO J. Am. Chem. Soc. 2023, 145, 50, 27295–27306
NO Ministerio de Ciencia e Innovación
DS Docta Complutense
RD 17 abr 2025