RT Journal Article
T1 Orbital Nature of Carboionic Monoradicals Made from Diradicals
A1 Cárdenas Valdivia, Abel
A1 Dai, Yasi
A1 Rambaldi, Filippo
A1 Barker, Joshua, E.
A1 Dressler, Justin J.
A1 Zhou, Zheng
A1 Zhu, Yikun
A1 Wei, Zheng
A1 Petrukhina, Marina A.
A1 Haley, Michael M.
A1 Casado-Cordón, Juan
A1 Negri, Fabrizia
K1 Hidrocarburos
AB The electronic, optical, and solid state properties of a series of monoradicals, anions and cations obtained from starting neutral diradicals have been studied. Diradicals based on s-indacene and indenoacenes, with benzothiophenes fused and in different orientations, feature a varying degree of diradical character in the neutral state, which is here related with the properties of the radical redox forms. The analysis of their optical features in the polymethine monoradicals has been carried out in the framework of the molecular orbital and valence bond theories. Electronic UVVis-NIR absorption, X-ray solid-state diffraction and quantumchemical calculations have been carried out. Studies of the different positive-/negative-charged species, both residing in the same skeletal π-conjugated backbone, are rare for organic molecules. The key factor for the dual stabilization is the presence of the starting diradical character that enables to indistinctively accommodate a pseudo-hole and a pseudoelectron defect with certainly small reorganization energies for ambipolar charge transport.
PB Wiley
YR 2023
FD 2023
LK https://hdl.handle.net/10630/26490
UL https://hdl.handle.net/10630/26490
LA eng
NO Cardenas Valdivia, Dai, Y., Rambaldi, F., Barker, J. E., Dressler, J. J., Zhou, Z., Zhu, Y., Wei, Z., Petrukhina, M. A., Haley, M. M., Negri, F., & Casado, J. (2023). Orbital Nature of Carboionic Monoradicals Made from Diradicals. Chemistry : a European Journal, e202300388–e202300388. https://doi.org/10.1002/chem.202300388
NO The authors thank the Spanish Ministry of Science and Innovation (projects MINECO/FEDER PGC2018-098533-B-100and PID2021-127127NB-I00) and the Junta de Andalucía, Spain (UMA18FEDERJA057 and Proyecto de Excelencia PROYEXCEL- 00328). We also thank the Research Central Services (SCAI) of the University of Málaga and the US National Science Foundation (CHE-1954389 to M.M.H., CHE-2003411 to M.A. P.). F.N and Y.D. acknowledge support from “Valutazione della Ricerca di Ateneo” (VRA)-University of Bologna. Y.D. acknowledges Ministero dell’Università e della Ricerca (MUR) for herPh.D. fellowship.Funding for open access charge: Universidad de Málaga / CBUA
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 19 ene 2026