Ion–π interaction in impacting the nonlinear optical properties of ion–buckybowl complexes

Abstract Ion–buckybowl complexes have received considerable attention in modern chemical research due to its fundamental and practical importance. Herein, we performed density functional theory (DFT) to calculate the geometical structure, binding interactions, dipole moments and the first hyperpolarizabilities ( β tot ) of ion–buckybowl complexes (ions are Cl − and Na + , buckybowls are quadrannulene, corannulene and sumanene). It is found that the stabilities of ion–buckybowl compounds primarily originate from the interaction energy, which was proved by a new isomerization energy decomposition analysis approach. Plots of reduced density gradient mirror the ion–π weak interaction has been formed between the ions and buckybowls. Significantly, the buckybowl subunits cannot effectively impact the nonlinear optical (NLO), but the kind of ion has marked influence on the second-order NLO responses. The β tot values of Cl − –buckybowl complexes are all larger as compared to that of Na + –buckybowl complexes, which is attributed to the large charge-transfer (CT) from Cl − to buckybowl. Our present work will be beneficial for further theoretical and experimental studies on the NLO properties of ion–buckybowl compounds.