Combination of Phthalocyanine, Azulene and Porphyrin for High Performance Nonlinear Optical Materials

Phthalocyanine and porphyrin derivatives have garnered extensive attention in nonlinear optics due to their large cyclic conjugation, tunable electronic structures, and excellent biocompatibility. In this work, polar azulene was employed to connect phthalocyanine and porphyrin to construct an asymmetric triadic structure for applications in nonlinear optics. The correlation between the designed molecular architecture and its nonlinear optical performance was systematically investigated through density functional theory based methods and the sum-over-states model. Under the synergistic effect of porphyrin modification, metal coordination, and electron-withdrawing group incorporation, the designed structures exhibit large static first and second hyperpolarizabilities (<β₀> and <γ₀>). Specifically, the <β₀> and <γ₀> of F₂BPcA_hMgP_(NH) reach -26957.00 × 10^-30 esu and -673.05 × 10^-34 esu, respectively. The strong nonlinear optical responses under external fields confer these materials potential applications in laser technology, optical communication, and biomedical fields. The proposed structure design strategy could facilitate the search for nonlinear optical materials for advanced applications.