3D Covalent Organic Frameworks from Design, Synthesis to Applications in Optoelectronics

Abstract Covalent organic frameworks (COFs), a new class of crystalline materials connected by covalent bonds, have been developed rapidly in the past decades. However, the research on COFs is mainly focused on two‐dimensional (2D) COFs, and the research on three‐dimensional (3D) COFs is still in the initial stage. In 2D COFs, the covalent bonds exist only in the 2D flakes and can form 1D channels, which hinder the charge transport to some extent. In contrast, 3D COFs have a more complex pore structure and thus exhibit higher specific surface area and richer active sites, which greatly enhance the 3D charge carrier transport. Therefore, compared to 2D COFs, 3D COFs have stronger applicability in energy storage and conversion, sensing, and optoelectronics. In this review, it is first introduced the design principles for 3D COFs, and in particular summarize the development of conjugated building blocks in 3D COFs, with a special focus on their application in optoelectronics. Subsequently, the preparation of 3D COF powders and thin films and methods to improve the stability and functionalization of 3D COFs are summarized. Moreover, the applications of 3D COFs in electronics are outlined. Finally, conclusions and future research directions for 3D COFs are presented.