π-Radical Cascade to a Chiral Saddle-Shaped Peropyrene

29 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via formation of multiple bonds and rings in a single step. Here, we explore the feasibility of using this “undesired” reaction of phenalenyl to build up strain and provide access to non-planar polycyclic aromatic hydrocarbons. To this end, we designed and synthesized a diradical system with two phenalenyl units linked via a biphenylene backbone. The design facilitates an intramolecular cascade reaction to a helically twisted saddle-shaped product, where the key transformations—ring-closure and ring-fusion—occur within one reaction. The negative curvature of the final peropyrene product, resulting from the presence of an eight-membered ring, was confirmed by single-crystal X-ray diffraction analysis and the helical twist was validated via resolution of the product’s enantiomers that display circularly polarized luminescence.

Keywords

phenalenyl
peropyrene
π-radical cascade
diradical
negative curvature
circularly polarized luminescence
saddle shape
helical chirality

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