RT Journal Article
T1 Tuneable stimuli-responsive behaviour, spectroscopic signatures and redox properties of indolo[3,2-b]carbazole-based diradicals
A1 Badía-Domínguez, Irene
A1 Wang, Deliang
A1 Nash, Rosie
A1 Hernández-Jolín, Víctor
A1 Collison, David
A1 Shanmugam, Muralidharan
A1 Hongxiang, Li
A1 Hartl, František
A1 Ruiz-Delgado, María del Carmen
K1 Reactividad (Química)
K1 Estructura química
AB 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.
PB RSC (Royal Society of Chemistry)
YR 2024
FD 2024-09-07
LK https://hdl.handle.net/10630/36143
UL https://hdl.handle.net/10630/36143
LA eng
NO 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-
NO Fuinding for open access charge: Universidad de Málaga
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 21 ene 2026