Abstract
We report persistent chiral organic mono- and diradical cations based on bicarbazole molecular design with an unprecedented stability dependence on the type of chirality, namely, axial versus helical. An unusual chemical stability was observed for sterically unprotected axial bicarbazole radical in comparison with monocarbazole and helical bicarbazole ones. Such results were experimentally and theoretically investigated, revealing an inversion in energy of the singly occupied molecular orbital (SOMO) and the highest (doubly) occupied molecular orbital (HOMO) in both axial and helical bicarbazole monoradicals along with a subtle difference of electronic coupling between the two carbazole units, which is modulated by their relative dihedral angle and related to the type of chirality. Such findings allowed us to explore in depth the SOMO-HOMO inversion (SHI) in chiral radical molecular systems and provide new insights regarding its impact on the stability of organic radicals. Finally, these specific electronic properties allowed us to prepare a persistent, intrinsically chiral, diradical which notably displayed near-infrared electronic circular dichroism responses up to 1100 nm and almost degenerate singlet-triplet ground states with weak antiferromagnetic interactions evaluated by magnetometry experiments.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.