Аннотация:Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However, the response of such materials toward laser-induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)-based porous COFs-Por-COF-HH and its dual metalated congeners Por-COF-ZnCu and Por-COF-ZnNi-have been prepared and present excellent NLO properties. Notably, intensity-dependent NLO switching behavior was observed for these Por-COFs, which is highly desirable for optical switching and optical limiting devices. Moreover, the efficient π-conjugation and charge-transfer transition in ZnCu-Por-COF enabled a high nonlinear absorption coefficient (β=4470 cm/GW) and figure of merit (FOM=σ1 /σo , 3565) value compared to other state-of-the-art materials, including molecular porphyrins (β≈100-400 cm/GW), metal-organic frameworks (MOFs; β≈0.3-0.5 cm/GW), and graphene (β=900 cm/GW).
