2026-05-29T21:20:43Zhttps://riuma.uma.es/rest/oai/requestoai:riuma.uma.es:10630/361432026-02-03T11:07:12Zcom_10630_2254col_10630_37953
RIUMA. Repositorio Institucional de la Universidad de Málaga
author
Badía-Domínguez, Irene
author
Wang, Deliang
author
Nash, Rosie
author
Hernández-Jolín, Víctor
author
Collison, David
author
Shanmugam, Muralidharan
author
Hongxiang, Li
author
Hartl, František
author
Ruiz-Delgado, María del Carmen
2025-01-10T13:26:00Z
2025-01-10T13:26:00Z
2024-09-07
Badía-Domínguez, Irene et al. “Tuneable Stimuli-Responsive Behaviour, Spectroscopic Signatures and Redox Properties of Indolo3,2-Bcarbazole-Based Diradicals.” Physical chemistry chemical physics : PCCP 26.41 (2024): 26238-
https://hdl.handle.net/10630/36143
10.1039/d4cp02729a
During the last decade, there has been an increasing interest in the rationalisation of how structural changes stabilise (or destabilise) diradical systems. Demonstrated herein is that indolocarbazole (ICz) diradicals, substituted with dicyanomethylene (DCM) groups, are useful motifs for dynamic covalent chemistry by self-assembling from isolated monomers to cyclophane structures. The comparison of ICz-based systems substituted with DCM groups in para-ormeta-positions (p-ICz-CN and m-ICz-CN) and their short-chain carbazole analogues (p-Cz-CN and m-Cz-CN) may identify new potential design strategies for stimuli-responsive materials. The principal objectives of this investigation are the elucidation of (i) the connection between diradical character and the cyclophane stability, (ii) the spatial disposition of the cyclophane structures, (iii) the monomer/cyclophane interconversion both in solution and solid state in response to external stimuli and (iv) the impact that the different p-conjugation and electronic communication between the DCM terminals exerts on the electronic adsorption of the diradicals and their redox behavior. The spontaneous nature of the cyclophane structure is supported by the negative relative Gibbs free energies calculated at 298 K and experimentally by UV-Vis and Raman spectroscopy of the initial yellow solid powder. The conversion to monomeric species having diradical character was demonstrated by variable-temperature (VT) EPR, UV-Vis, Raman and IR measurements, resulting in appreciable chromic changes. In addition, electrochemical oxidation and reduction convert the cyclophane dimer (m-ICz-CN)2 to the monomer monocations and dianions, respectively. This research demonstrates how the chemical reactivity and physical properties of p-conjugated diradicals can be effectively tuned by subtle changes in their chemical structures.
eng
Atribución 4.0 Internacional
Reactividad (Química)
Estructura química
Tuneable stimuli-responsive behaviour, spectroscopic signatures and redox properties of indolo[3,2-b]carbazole-based diradicals
journal article
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