Abstract
Conjugated microporous polymers (CMPs) are a unique class of materials that combine extended π-conjugation with a permanently microporous skeleton. Since their discovery in 2007, CMPs have become established as an important subclass of porous materials. A wide range of synthetic building blocks and network-forming reactions offers an enormous variety of CMPs with different properties and structures. This has allowed CMPs to be developed for gas adsorption and separations, chemical adsorption and encapsulation, heterogeneous catalysis, photoredox catalysis, light emittance, sensing, energy storage, biological applications, and solar fuels production. Here we review the progress of CMP research since its beginnings and offer an outlook for where these materials might be headed in the future. We also compare the prospect for CMPs against the growing range of conjugated crystalline covalent organic frameworks (COFs).
Highlights
Conjugated microporous polymers (CMPs) are a unique class of materials that combine extended π-conjugation with a permanently microporous skeleton
Porous organic cages (POCs) are discrete porous molecules where the molecular cage is synthesized first and assembled in the solid state in a separate step.[6−8] porous organic cages (POCs) are a unique class of solutionprocessable molecular materials where porosity arises via interconnection of intrinsic cavities, which can be modified by changing the solid state packing of the cage molecules
porous aromatic frameworks (PAFs),[22−24] which are closely related to CMPs and formed using similar coupling chemistries, do not possess extended π-conjugation because they are linked by tetrahedral tetraphenylmethane nodes
Summary
Davankov et al reported the first example of hypercrosslinked polymers[31] in 1969, before either of the coauthors of this review were born. The optical band gap in CMPs allows opportunities in photocatalysis.[44,63,64] In 2015, our group reported a series of CMP networks that exhibit photocatalytic H2 evolution from water, in the presence of a sacrificial electron donor, without any additional metal catalysts.[52] The optical gap in these networks could be tuned over a wide range in continuous fashion by varying the monomer composition These CMPs are potentially advantageous in comparison to linear conjugated polymers, which are often poorly active in visible light, and graphitic carbon nitrides, where it is challenging to tune the optical gap.[65,66].
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