Macroscale Conjugated Microporous Polymers: Controlling Versatile Functionalities Over Several Dimensions

Since discovered in 2007, conjugated microporous polymers (CMPs) have been developed for numerous applications including gas adsorption, sensing, organic and photoredox catalysis, energy storage, etc. While featuring abundant micropores, the structural rigidity derived from CMPs’ stable π‐conjugated skeleton leads to insolubility and thus poor processability, which severely limits their applicability, e.g., in CMP‐based devices. Hence, the development of CMPs whose structure can not only be controlled on the micro‐ but also on the macroscale have attracted tremendous interest. In conventional synthesis procedures, CMPs are obtained as powders, but in recent years various bottom‐up synthesis strategies have been developed, which yield CMPs as thin films on substrates or as hybrid materials, allowing to span length scales from individual conjugated monomers to micro‐/macrostructures. This review surveys recent advances on the construction of CMPs into macroscale structures, including membranes, films, aerogels, sponges, and other architectures. The focus is to describe the underlying fabrication techniques and the implications which follow from the macroscale morphologies, involving new chemistry and physics in such materials for applications like molecular separation/filtration/adsorption, energy storage and conversion, photothermal transformation, sensing, or catalysis. Recent progress in macroscale conjugated microporous polymers for gas adsorption, energy, sensing, filtration/purification, and catalysis applications are reviewed, with particular focus on how the macroscopic architectures brings about more functionalities and opportunities.