2026-06-03T08:20:43Zhttps://riuma.uma.es/rest/oai/requestoai:riuma.uma.es:10630/248132026-02-03T11:36:22Zcom_10630_2254col_10630_37953
RIUMA. Repositorio Institucional de la Universidad de Málaga
author
Badía-Domínguez, María Irene
author
Canola, Sofía
author
Hernández-Jolín, Víctor
author
López-Navarrete, Juan Teodomiro
author
Sancho-García, Juan C.
author
Negri, Fabrizia
author
Ruiz-Delgado, María del Carmen
2022-08-25T07:32:20Z
2022-08-25T07:32:20Z
2022-06-23
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
https://hdl.handle.net/10630/24813
10.1021/acs.jpclett.2c01325
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.
eng
Atribución 4.0 Internacional
Estructura química
Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position
journal article
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568d95503239a2164659f91f43a35310
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acs.jpclett.2c01325.pdf