Swiss Science Concentrates

of Zurich This study challenges the conventional perception of open-shell molecular graphene fragment reactions as undesired decomposition processes, showcasing their potential as synthetic tools for the costruction of complex nanostructures.The oxidative dimerization of phenalenyl to peropyrene serves as an example, demonstrating the formation of multiple bonds and a ring in a single step.The investigation explores the 'undesired' reaction of phenalenyl to introduce strain, leading to the synthesis of nonplanar polycyclic aromatic hydrocarbon.A biradical system with two phenalenyl units linked via a biphenylene backbone was designed for this purpose.Intramolecular cascade reactions facilitated the formation of a helically twisted saddle-shaped product, involving key transformations like ring-closure and ring-fusion.Single-crystal X-ray diffraction confirmed the product's negative curvature induced by an eight-membered ring, while the resolution of enantiomers revealed circularly polarized luminescence and high configurational stability, validating the success of the synthetic approach.