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Covalent organic frameworks: a materials platform for structural and functional designs

Abstract

Covalent organic frameworks (COFs) are a class of crystalline porous polymer that allows the atomically precise integration of organic units into extended structures with periodic skeletons and ordered nanopores. One important feature of COFs is that they are designable; that is, the geometry and dimensions of the building blocks can be controlled to direct the topological evolution of structural periodicity. The diversity of building blocks and covalent linkage topology schemes make COFs an emerging materials platform for structural control and functional design. Indeed, COF architectures offer confined molecular spaces for the interplay of photons, excitons, electrons, holes, ions and guest molecules, thereby exhibiting unique properties and functions. In this Review, we summarize the major progress in the field of COFs and recent achievements in developing new design principles and synthetic strategies. We highlight cutting-edge functional designs and identify fundamental issues that need to be addressed in conjunction with future research directions from chemistry, physics and materials perspectives.

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Figure 1: Diversity of linkages for the formation of COFs.
Figure 2: Typical building blocks used to synthesize boronate ester and boroxine-linked COFs.
Figure 3: Typical building blocks used to form imine-, hydrazone-, azine-, squaraine- and phenazine-linked COFs.
Figure 4: Methods to control stability and crystallinity.
Figure 5: Pore design in COFs.
Figure 6: Functional exploration of skeletons in COFs.
Figure 7: Complementary design of pores and skeletons in COFs.

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Huang, N., Wang, P. & Jiang, D. Covalent organic frameworks: a materials platform for structural and functional designs. Nat Rev Mater 1, 16068 (2016). https://doi.org/10.1038/natrevmats.2016.68

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