@misc{10481/92345,
year = {2024},
month = {3},
url = {https://hdl.handle.net/10481/92345},
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 biradical 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, induced by the formed eightmembered
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 and high configurational
stability.},
organization = {H2020 European Research Council. Grant Number: ERC StG 716139 / INSPIRAL},
organization = {Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung. Grant Numbers: CRSK-2_190365, PP00P2_170534, PP00P2_198900, TMCG-2_213829 / CASCADER},
organization = {Universität Zürich. Grant Number: FK-21-131},
organization = {Deutsche Forschungsgemeinschaft. Grant Number: 417643975},
organization = {Open Access funding provided by Universität Zürich.},
publisher = {Wiley},
keywords = {Circularly polarized luminescence},
keywords = {Chirality},
title = {π-Radical Cascade to a Chiral Saddle-Shaped Peropyrene},
doi = {10.1002/anie.202318254},
author = {Bernhardt, Annika and Čavlović, Daniel and Mayländer, Maximilian and Blacque, Olivier and Moreno Cruz, Carlos and Richert, Sabine and Juríček, Michal},
}