3D Covalent Organic Frameworks with 16-Connectivity for Photocatalytic C(sp3)–C(sp2) Cross-Coupling

The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher connectivity remains a great challenge in the field of COF structural design. Herein, this work reports a hierarchical expansion strategy for making 16-connected building blocks to construct 3D COFs with sqc topology. The [16 + 2] construction achieved by condensation between a 16-connected carbazolyl dicyanobenzene-based building block (CzTPN) and linear diamino linkers (BD or Bpy) affords two 3D COFs (named CzBD COF and CzBpy COF). Furthermore, attributed to the well-organized donor-acceptor (D-A) heterojunction, the Ni chelated CzBpy COF (Ni@CzBpy COF) exhibits excellent performance for photoredox/Ni dual catalytic C(sp