RT Journal Article
T1 Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position
A1 Badía-Domínguez, María Irene
A1 Canola, Sofía
A1 Hernández-Jolín, Víctor
A1 López-Navarrete, Juan Teodomiro
A1 Sancho-García, Juan C.
A1 Negri, Fabrizia
A1 Ruiz-Delgado, María del Carmen
K1 Estructura química
AB In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet–triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.
PB American Chemical Society
YR 2022
FD 2022-06-23
LK https://hdl.handle.net/10630/24813
UL https://hdl.handle.net/10630/24813
LA eng
NO Badía Domínguez, María Irene ; Canola, Sofía ; Hernández-Jolín, Víctor ; López Navarrete, Juan T. ; Sancho-García, Juan C. ; Negri, Fabrizia ; Ruíz-Delgado, María del Carmen. Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position. J. Phys. Chem. Lett. 2022, 13, 26, 6003–6010 Publication Date:June 23, 2022 https://doi.org/10.1021/acs.jpclett.2c01325
NO Funding for open access charge: Univesidad de Málaga/CBUA.
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 21 ene 2026