Red Emissive Double Aza[7]helicenes with Antiaromaticity / Aromaticity Switching via the Redox‐Induced Radical Cation and Dication Species

Abstract

AbstractWe herein present the synthetic approach to a new antiaromatic double aza[7]heliceneCthat features NN‐embedded polycyclic aromatic hydrocarbons (PAHs). This heteroatom‐doped helicene showed a rarely obtained long‐wavelength emission and far‐red circularly polarized luminescence (CPL) in the solid state. These optical and chiroptical properties could be ascribed to both the NN‐PAH core structure and the further extension through angular ring fusions. Such a unique electronic structure also culminated in facile chemical oxidations of neutralCto the positively charged chiral radical (C⋅+) and dication species (C2+). Interestingly, DFT computations revealed that the pyridazine central core showed an antiaromaticity‐to‐aromaticity switching, in contrast to the inversed transition for the helical periphery in cationic states. The reported approaches are anticipated to lead to the development of further redox‐active chiral systems for potential applications in chiroptoelectronics, spintronics as well as fluorescent bioimaging.