The photochemical cyclodehydrochlorination (CDHC) reaction has recently been used to prepare a wide variety of polycyclic aromatic hydrocarbons and graphene nanoribbons (GNRs). However, the parameters affecting the efficiency of this reaction have been scarcely studied. In this work, we investigated how the reaction conditions influence the outcome of the reaction. The effect of functional groups on the different phenyl rings of the o-terphenyl scaffold was also studied. The reaction kinetics follow the same trend as Hammett's constant when electron-donating and electron-withdrawing groups are present on the ring bearing the chlorine. The CDHC reaction can be successfully performed using less energetic 365 nm light in the presence of a triplet sensitizer. Computational results provide insight on the reaction mechanism, notably by identifying its three intermediate structures as well as its limiting step.
Keywords: Cyclization; C−C coupling; Photochemistry; Polycyclic aromatic hydrocarbons.
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