RT Journal Article
T1 Photofunctional Scope of Fluorescent Dithienylethene Conjugates with Aza-Heteroaromatic Cations
A1 Chen Wu, Jialei
A1 Guzmán Ríos, David Benjamín
A1 Remón Ruiz, Patricia
A1 González-Delgado, José Antonio
A1 Martínez Martínez, Antonio Jesús
A1 Nájera, Francisco
A1 Fernández Arteaga, Jesús
A1 Pischel, Uwe
AB A series of dithienylethene (DTE) photoswitches with aza-heteroaromatic cationic moieties is synthesized. The switches are characterized regarding their photochemical and photophysical properties in acetonitrile and in water. The efficiency of the switching and the photostationary state composition depend on the degree of π-conjugation of the heteroaromatic systems. Thus, DTEs with acridinium-derived moieties have very low quantum yields for the ring-closing process, which is in contrast to switches with pyridinium and quinolinium moieties. All switches emit fluorescence in their open forms. The involved electronic transitions are traced back to an integrative picture including the DTE core and the cationic arms. The emission can be fine-tuned by the π-conjugation of the heteroaromatic cations, reaching the red spectral region for DTEs with acridinium moieties. On ring-closing of the DTEs the fluorescence is not observable anymore. Theoretical calculations point to rather low-lying energy levels of the highly conjugated ring-closed DTEs, which would originate near-infrared emission (> 1200 nm). The latter is predicted to be very weak due to the concurrent non-radiative deactivation, according to the energy-gap law. In essence, an ON-OFF fluorescence switching as the result of the electrocyclic ring-closing reaction is observed.
PB Wiley
SN 0935-9648
SN 1521-4095 (electrónico)
YR 2023
FD 2023-04
LK https://hdl.handle.net/10272/22436
UL https://hdl.handle.net/10272/22436
LA eng
NO Chen‐Wu, J., Guzmán‐Ríos, D. B., Remón, P., González‐Delgado, J. A., Martínez‐Martínez, A. J., Nájera, F., Arteaga, J. F., & Pischel, U. (2023). Photofunctional Scope of Fluorescent Dithienylethene Conjugates with Aza‐Heteroaromatic Cations. In Advanced Materials (Vol. 35, Issue 28). Wiley. https://doi.org/10.1002/adma.202300536
NO The authors acknowledge the financial support by the Spanish Ministerio de Ciencia e Innovación (grant PID2020-119992GB-I00 for U.P., PID2019-104293GB-I00 for F.N., PID2019-108292RA-I00, EUR2020-112189 for A.J.M.-M.), the Consejería de Universidad, Investigación e Innovación/Junta de Andalucía (grant P18-FR-4080 for U.P.), the EuropeanResearch and Development Fund (ERDF), and the Junta de Andalucía / University of Huelva (grant UHU-202070 for U.P.). A.J.M.-M. thanks the AEI Research State Agency for a Ramón y Cajal research contract (RYC-2017-21783). The authors are indebted to the Supercomputing and Bioinformatics Centre (SCBI) of the University of Málaga for makingavailable the computer resources that were employed for the theoretical calculations.
DS Repositorio Institucional de la Universidad de Huelva
RD 13 jun 2026