Three-Dimensional Covalent Organic Frameworks with jcg Topology Based on a Trinodal Strategy

The development of three-dimensional (3D) covalent organic frameworks (COFs) holds significant promise for various applications, but the conventional uninodal or binodal design strategies limit their structural diversity. In this work, we present a novel trinodal strategy for the synthesis of 3D COFs featuring both microporous and mesoporous nanochannels. Using powder X-ray diffraction (PXRD), computational simulations, and high-resolution transmission electron microscopy (HR-TEM), we demonstrate that employing an 8-c building block with reduced symmetry, which can be considered as 4- and 3-connected subunits, along with planar 4-c building blocks, results in an unprecedented [4 + 3 + 4]-c jcg net. This structure features rare saddle-shaped eight-membered rings and mirror-symmetrical chains. Furthermore, the incorporation of chromophore pyrene and redox-active triphenylamine components, coupled with structural conjugation, imparts tunable photophysical and electronic properties to these COFs, making them promising candidates for photocatalytic H 2 O 2 production. This work highlights the potential of the trinodal strategy in creating intricate COF architectures and enhances their applicability in heterogeneous photocatalysis.