RT Journal Article
T1 Dynamic Covalent Properties of a Novel Indolo[3,2-b]carbazole Diradical
A1 Badía-Domínguez, Irene
A1 Peña-Álvarez, Miriam
A1 Wang, Deliang
A1 Pérez Guardiola, Andrés
A1 Vida-Pol, Yolanda
A1 Rodríguez-González, Sandra
A1 López Navarrete, Juan T.
A1 Hernández-Jolín, Víctor
A1 Sancho-García, Juan C.
A1 García-Baonza, Valentín
A1 Nash, Rosie
A1 Hartl, František
A1 Li, Hongxiang
A1 Ruiz-Delgado, María del Carmen
K1 Espectroscopia
AB This work describes the synthesis and properties of a dicyanomethylene-substituted indolo[3,2-b]carbazole diradical ICz-CN. This quinoidal system dimerises almost completely to (ICz-CN)2, which contains two long C(sp3)−C(sp3) σ-bonds between the dicyanomethylene units. The minor open-shell ICz-CN component in the solid-state mixture was identified by EPR spectroscopy. Cyclic voltammetry and UV–visible spectroelectrochemical data, as well as comparison with reference monomer ICz-Br reveal that the nature of the one-electron oxidation of (ICz-CN)2 at ambient temperature and ICz-CN at elevated temperature is very similar in all these compounds due to the prevailing localization of their HOMO on the ICz backbone. The peculiar cathodic behaviour reflects the co-existence of (ICz-CN)2 and ICz-CN. The involvement of the dicyanomethylene groups stabilizes the close-lying LUMO and LUMO+1 of (ICz-CN)2 and especially ICz-CN compared to ICz-Br, resulting in a distinctive cathodic response at low overpotentials. Differently from neutral ICz-CN, its radical anion and dianion are remarkably stable under ambient conditions. The UV/Vis(–NIR) electronic transitions in parent (ICz-CN)2 and ICz-CN and their different redox forms have been assigned convincingly with the aid of TD-DFT calculations. The σ-bond in neutral (ICz-CN)2 is cleaved in solution and in the solid-state upon soft external stimuli (temperature, pressure), showing a strong chromism from light yellow to blue–green. Notably, in the solid state, the monomeric diradical species is predominantly formed under high hydrostatic pressure (>1 GPa).
PB Wiley
YR 2021
FD 2021
LK https://hdl.handle.net/10630/34454
UL https://hdl.handle.net/10630/34454
LA eng
NO I. Badía-Domínguez, M. Peña-Álvarez, D. Wang, A. Pérez Guardiola, Y. Vida, S. Rodríguez González, J. T. López Navarrete, V. Hernández Jolín, J. C. Sancho García, V. García Baonza, R. Nash, F. Hartl, H. Li, M. C. Ruiz Delgado, Dynamic Covalent Properties of a Novel Indolo[3,2-b]carbazole Diradical. Chem. Eur. J. 2021, 27, 5509.
NO Ministerio de Ciencia, Innovación y Universidades. Grant Numbers: PID2019-110305GB-I00, PID2019-106114GB-I00, PID2019-104293GB-I00, PCI2019-111825-2Agencia de Innovación y Desarrollo de Andalucía. Grant Numbers: UMA18-FEDERJA-080, P09FQM-4708, UMA18-FEDERJA-007Universidad de Málaga. Grant Number: Ayuda para la incorporación de doctoresConselleria d'Educació, Investigació, Cultura i Esport. Grant Number: AICO/2018/175National Natural Science Foundation of China. Grant Number: 21875279 and 21790362H2020 European Research Council. Grant Number: 695527Ministerio de Economía, Industria y Competitividad, Gobierno de España. Grant Number: CTQ2013-48252-P, CTQ2015-67755-C02-01-R and PGC2018-094814-B-C21Instituto de Salud Carlos III (ISCIII). Grant Number: RETIC ARADYAL, RD16/0006/0012
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 19 ene 2026