A strategy to design nonlinear optical materials: Self‐assembling by π ‐ π stacking

Abstract Lacking high‐performance nonlinear optical (NLO) materials limits the applications to opto‐electronic devices. In this work, a strategy of self‐assembling driven by π‐π stacking is proposed to design high‐performance NLO materials. Here, the third‐order NLO responses of two carbon‐based fuller‐rylenes dimers ( Fuller‐PMI and Fuller‐PDI ) are theoretically studied. The results mainly highlight the following points: (1) these two dimers are in good thermodynamic and kinetic stability, and the interaction energies of Fuller‐PMI and Fuller‐PDI dimers have reached to −63.50 kcal/mol and −68.18 kcal/mol, respectively; (2) the ratios of the static second order hyperpolarizability (, i∈{x, y, z}) between the dimer and the monomer are = 5.5, = 1.2 and = 1.2 for Fuller‐PMI , = 1.1, =1.4 and = 4.2 for Fuller‐PDI . These results demonstrate that the self‐assembling driven by π‐π stacking is an effective strategy for designing high‐performance NLO materials.