Abstract/Summary

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- or meta-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.