Phthalocyanine Covalent Organic Frameworks: Dimensionality Effect on Third‐Order Nonlinear Optical Properties

Abstract Dimensionality of covalent organic frameworks (COFs), in terms of 2D and 3D, must greatly influence their properties and functionalities due to the different electronic and porous structures, but still less investigated in the 20 years history. Herein, on the basis of the imidization reaction of phthalocyanine‐based tetraanhydride monomers with either 1,4‐phenylenediamine or 1,3,5,7‐tetra(4‐aminophenyl)adamantine, 2D and 3D imide‐bonded COFs with sql and pts topology have been prepared to explore their third‐order nonlinear optical (NLO) properties. In contrast to metal‐free analogues, both 2D and 3D copper‐phthalocyanine COFs have the enhanced NLO behaviors according to the open aperture Z‐scan and optical limiting (OL) results recorded under a nanosecond laser at 532 nm. In particular, 2D COFs with strong π – π staking phthalocyanine units show the NLO property with bigger third‐order nonlinear susceptibility ( Imχ ⁽³⁾ ) and unique reverse saturation absorption response at 1064 nm than that of 3D species with dispersed conjugated modules. Furthermore, femtosecond transient absorption spectra disclose the longer excited lifetimes of copper COFs than metal free samples, helpful in their NLO property. These findings clearly disclose the materials advantages of 2D phthalocyanine COFs toward the NLO characteristics and provide new candidates for OL application.