2D Conjugated Covalent Organic Frameworks: Defined Synthesis and Tailor-Made Functions

Covalent organic frameworks (COFs) are an emerging class of crystalline porous polymers and have received tremendous attention and research interest. COFs can be classified into two-dimensional (2D) and three-dimensional (3D) analogues. Resembling the architectures of porous graphene, 2D conjugated COFs have exhibited promising prospects in many fields, such as gas storage and separation, heterogeneous catalysis, sensing, photocatalysis, environmental remediation, drug delivery, energy storage and conversion, and so forth. However, efficient structural design for high-throughput production of crystalline 2D COFs remains challenging. In this Account, we summarize our recent contributions to the design, synthesis, and application exploration of 2D conjugated COFs. First, we raised an efficient "two-in-one" strategy for the facile synthesis of 2D imine COFs with good reproducibility and solvent adaptability. Thanks to this elaborate molecular design strategy, we could easily modulate the topology of COFs and fabricate COF films. In addition, we developed two approaches to stabilize the 2D conjugated COFs by using planar building blocks and donor-acceptor structures. We also proposed a skeleton engineering strategy to design COFs as electrode materials, through which redox-active orthoquinone moieties were stepwise-incorporated in the skeletons of isostructural 2D imine-linked COFs. This strategy enabled systematic investigations on a series of 2D conjugated COFs with analogous structures but different numbers of active sites for energy storage, which provides a good platform to unveil the underlying structure-property relationships. In addition, we recently developed a new kind of arylamine-linked 2D conjugated COFs. The electroactive diphenylamine linkages endowed these 2D conjugated COFs with extended conjugation and improved stability, which also conferred these COFs with excellent pseudocapacitive energy storage performance. Moreover, tailor-made sulfur-rich COFs were introduced that were synthesized by selective introduction of polysulfide or sulfonyl groups on the COF skeletons and were used for Li storage and proton conduction. At the end, the key challenges of 2D conjugated COFs toward practical applications and their future prospects are suggested. We hope that this Account will evoke new inspirations and innovative work in the field of 2D conjugated COFs in the near future, especially in some burgeoning and interdisciplinary research areas.