Adding multiple electrons to helicenes: how they respond?

Abstract

Helicenes of increasing dimensions and complexity have recently burst into the scene due to their unique structures coupled with interesting chiral, optical, and conducting properties. The helicene-related research has quickly progressed from fundamental curiosity to a diverse range of applications in organic catalysis, optoelectronic devices, chiroptical switches, sensors, and energy storage. The in-depth understanding of electron accepting properties of helicenes should further advance their materials chemistry applications, however, previous reports only relied on spectrocopic and electrochemical studies, while their structural changes weren't extensively discussed. Therefore, we initiated a broad investigation of chemical reduction behaviour of helicenes ranging in size and properties coupled with X-ray diffraction characterization of the reduced products. The responses of helicenes with different structures to the stepwise electron addition were investigated using a combination of X-ray crystallography, spectroscopic methods, and calculations. This study revealed topology- and charge-dependent consequences of chemical reduction ranging from reversible geometry perturbation to irreversible core transformation and site-specific reactivity of helicenes in addition to original alkali metal coordination patterns. This overview is focused on the crystallographically confirmed examples stemming from chemical reduction reactions of different helicenes with alkali metals. The opened discussion should stimulate further exploration of reactivity and complexation of novel π-expanded and heteroatom-doped helicenes based on the revealed structure–property correlations, thus advancing their applications as intriguing new materials.