The curved and electron-rich nature of buckybowls doped with heteroatoms makes them suitable electron-donating hosts for fullerene in the formation of concave–convex supramolecular complexes. The bowl depths of heteroatom-doped buckybowls are sensitive for the radius of the doping atoms. With the aim to investigate the influence of the bowl depth of the buckybowl and intermolecular interaction on the nonlinear optical (NLO) responses of complexes, the structures, binding interactions, electronic absorption spectra, and first hyperpolarizabilities (βtot) of the complexes formed by X-doped sumanene (X= Si, Ge, O, S, and Se) and C60 have been explored using density functional theory calculations. It is found that as doped atoms’ radii increase, the curvatures with shallower bowl depth of buckybowls and the distance between the base of C60 and buckybowls become increasingly smaller. However, atoms with larger radius tend to produce stronger binding energies between buckybowls and C60, accompanied with a gradual increase of their βtot values, which is due to that smaller layer spacing and stronger intermolecular interaction resulted in the lower transition energy of the crucial excited state. The results presented in this Article provide important evidence for the convex–convex interaction in enhancing the NLO properties. Thus, controlling the intermolecular interaction is important in terms of designing novel smart NLO materials.

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