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, José Manuel
A1 Suarez-Blas, Fátima
A1 Clarke, Tracey M.
A1 Kang, Seongsoo
A1 Oh, Juwon
A1 Ramos, M. Mar
A1 Kim, Dong-Ho
A1 Casanova, David
A1 Segura, José L.
A1 Casado-Cordón, Juan
K1 Química física
K1 Bases (Química)
K1 Moléculas
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 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.
PB ACS
YR 2023
FD 2023-12-20
LK https://hdl.handle.net/10630/30240
UL https://hdl.handle.net/10630/30240
LA eng
NO Samara Medina Rivero, Matías J. Alonso-Navarro, Claire Tonnelé, Jose M. Marín-Beloqui, Fátima Suárez-Blas, Tracey M. Clarke, Seongsoo Kang, Juwon Oh, M. Mar Ramos, Dongho Kim, David Casanova, José L. Segura, and Juan Casado Journal of the American Chemical Society 2023 145 (50), 27295-27306 DOI: 10.1021/jacs.3c06916
NO Funding for open Access charge: Universidad de Málaga / CBUA.The authors thank the Spanish Ministry of Science andInnovation (projects MICIN/FEDER PID2021-127127NB-I00, PID2019-109555GB-I00, PID2022-136231NB-I00,PID2022-138908NB-C33, and TED2021-129886B−C43),the Junta de Andalucía (PROYEXCEL-0328), and the EuskoJaurlaritza (project PIBA19-0004).
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 23 ene 2026