Three-Dimensional Fully Conjugated Covalent Organic Frameworks from a Hexaconnected sp²-Carbon Building Unit.

). Furthermore, the 3D-CDHTh-COFs demonstrate outstanding photocatalytic performance, as evidenced by the highly efficient and selective aerobic oxidation of thioanisole (up to 99%). This work not only introduces a pioneering architecture for high-connected conjugated building blocks but also establishes a new platform of 3D full conjugated COFs with significant potential in optoelectronics and heterogeneous photocatalysis.