Here, the mislinked expanded porphyrins singly (labeled A) and doubly (labeled B) neo-confused [22]­smaragdyrin, the boron-dipyrromethenes-based mislinked expanded porphyrins singly (labeled C) and doubly (labeled D) neo-confused [22]­smaragdyrin, where both C and D include a −BF2 group, are chosen to serve as the study objects, and theoretical calculations are carried out to study the role of the −BF2 group in the second-order nonlinear optics (NLO) behaviors. Results highlighted that the −BF2 group plays an important role for the second-order behaviors in mislinked expanded porphyrins; namely, embedding the −BF2 group well enhanced the hyper-Rayleigh scattering (HRS) value {βHRS(0;0,0)}, = 2.0 and = 2.9, main owning to the fact that installing −BF2 increases the electron delocalization degree and decreases the excited energy of the crucial excited state.

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 (γiiiiFF, i∈{x, y, z}) between the dimer and the monomer are γxxxxFF()dimerγxxxxFF()monomer = 5.5, γyyyyFF()dimerγyyyyFF()monomer = 1.2 and γzzzzFF()dimerγzzzzFF()monomer = 1.2 for Fuller‐PMI, γxxxxFF()dimerγxxxxFF()monomer = 1.1, γyyyyFF()dimerγyyyyFF()monomer =1.4 and γzzzzFF()dimerγzzzzFF()monomer = 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.