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

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‐PMIand 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‐PMIand Fuller‐PDIdimers 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 γxxxxFFdimerγxxxxFFmonomer= 5.5, γyyyyFFdimerγyyyyFFmonomer= 1.2 and γzzzzFFdimerγzzzzFFmonomer= 1.2 for Fuller‐PMI, γxxxxFFdimerγxxxxFFmonomer= 1.1, γyyyyFFdimerγyyyyFFmonomer=1.4 and γzzzzFFdimerγzzzzFFmonomer= 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. The self‐assembling strategy induced by π‐π stacking is utilized to design nonlinear optical (NLO) materials. Results suggest that this strategy is a very effective for designing high performance NLO materials. In this work, self‐assembly driven by π‐π stacking designs NLO materials with the remarkable second hyperpolarizability.