ConspectusSince the first report of conjugated microporous polymers (CMPs) by Lee and Cooper in 2007, these porous materials have attracted intense interest due to their precisely tunable pore structures, rigid skeletons, chemical stability, and electronic properties. Researchers have developed various synthetic strategies for CMPs, including Yamamoto, Suzuki, and Sonogashira–Hagihara coupling reactions. However, these C–C coupling reactions often limit the structural diversity and high performance of CMPs, primarily due to the rigid linear or planar geometries imposed by the alkyne and aryl building blocks, which restrict the control over porosity and electronic properties in the meantime. Although C–C coupling reactions represent one of the most common strategies for synthesizing CMPs, their harsh reaction requirements also limit the development of CMPs for practical applications.Buchwald–Hartwig (BH) cross-coupling is a powerful strategy that directly addresses shortcomings of traditional coupling reactions by the formation of C–N instead of C–C bonds. First, the rotatable C–N bond and nonlinear amine monomers allow for the creation of various three-dimensional (3D) network architectures. The introduction of nitrogen heteroatoms effectively tunes the charge density, acts as an electrochemical active center for redox reactions, and allows for facile functionalization. Additionally, the reaction proceeds under mild conditions, which enables easy control over the polymerization process. Our group has been working on CMP synthesis for years, particularly by BH cross-coupling. In 2014, our group used BH cross-coupling to construct polytriphenylamine CMPs in the first report of CMP synthesized by BH cross-coupling. Since then, various CMPs with innovative macroscopic structural designs, including porous membranes, fibers, and carbons, were synthesized by BH cross-coupling, exhibiting an enhanced performance in adsorption, catalysis, energy storage, and desalination.Although various reviews have been reported on the synthesis and applications of CMPs, a few of them have focused on using BH cross-coupling to synthesize CMPs. Therefore, this review summarizes recent research progress on CMP synthesis via BH cross-coupling, with emphasis on monomer selection, reaction conditions, structural design and applications in the energy and environmental fields. More specifically, the review begins by tracing the development of the BH cross-coupling and its application in CMP synthesis. It then summarizes the preparation methods and applications of macroscopic CMPs, including porous membranes, fibers, and carbons. Finally, the current challenges of this method are discussed along with proposed future directions. Overall, the BH cross-coupling, with the advantages of mild reaction conditions, high yields, and precise control over structural diversity, provides a new strategy for constructing structurally tunable and high-performance CMPs. This approach is expected to play a significant role in macroscopic device integration and sustainable energy and environmental technologies.
Hou et al. (Mon,) studied this question.