Persistent, highly localized, and tunable [4]helicene radicals.

Chemical Science
Aslam ShaikhThomas Gianetti

Abstract

Persistent organic radicals have gained considerable attention in the fields of catalysis and materials science. In particular, helical molecules are of great interest for the development and application of novel organic radicals in optoelectronic and spintronic materials. Here we report the syntheses of easily tunable and stable neutral quinolinoacridine radicals under anaerobic conditions by chemical reduction of their quinolinoacridinium cation analogs. The structures of these [4]helicene radicals were determined by X-ray crystallography. Density functional theory (DFT) calculations, supported by electron paramagnetic resonance (EPR) measurements, indicate that over 40% of spin density is located at the central carbon of our [4]helicene radicals regardless of their structural modifications. The localization of the charge promotes a reversible oxidation to the cation upon exposure to air. This unusual reactivity toward molecular oxygen was monitored via UV-Vis spectroscopy.

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Citations

Sep 18, 2021·Organic Letters·Agnieszka BodziochPiotr Kaszyński
Nov 19, 2021·The Journal of Organic Chemistry·Jesper Dahl JensenBo W Laursen

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Methods Mentioned

BETA
electron paramagnetic resonance
electron-nuclear double resonance
X-ray
NMR
ENDOR

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