ABSTRACT
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 365â 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.
ABSTRACT
Richardson-Gaudin (RG) states are employed as a variational wave function ansatz for strongly correlated isomers of H4 and H10. In each case, a single RG state describes the seniority-zero sector quite well. Simple natural orbital functionals offer a cheap and reasonable approximation of the outstanding weak correlation in the seniority-zero sector, while systematic improvement is achieved by performing a configuration interaction in terms of RG states.
