Chiral Peropyrene: Synthesis, Structure, and Properties

• Published in: Journal of the American Chemical Society Vol. 139; no. 37; pp. 13102 - 13109
• Main Authors: Yang, Wenlong, Longhi, Giovanna, Abbate, Sergio, Lucotti, Andrea, Tommasini, Matteo, Villani, Claudio, Catalano, Vincent J, Lykhin, Aleksandr O, Varganov, Sergey A, Chalifoux, Wesley A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 20-09-2017
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.7b06848

Herein we describe the synthesis, structure, and properties of chiral peropyrenes. Using p-terphenyl-2,2″,6,6″-tetrayne derivatives as precursors, chiral peropyrenes were formed after a 4-fold alkyne cyclization reaction promoted by triflic acid. Due to the repulsion of the two aryl substituents within the same bay region, the chiral peropyrene adopts a twisted backbone with an end-to-end twist angle of 28° that was unambiguously confirmed by X-ray crystallographic analysis. The chiral peropyrene products absorb and emit in the green region of the UV–visible spectrum. Circular dichroism spectroscopy shows strong Cotton effects (Δε = ±100 M–1 cm–1 at 300 nm). The Raman data shows the expected D-band along with a split G-band that is due to longitudinal and transversal G modes. This data corresponds well with the simulated Raman spectra of chiral peropyrenes. The chiral peropyrene products also display circularly polarized luminescence. The cyclization reaction mechanism and the enantiomeric composition of the peropyrene products are explained using DFT calculations. The inversion barrier for racemization was determined experimentally to be 29 kcal/mol and is supported by quantum mechanical calculations.