Summary
Covalent organic frameworks (COFs) are a class of materials that form two- or three-dimensional structures through reactions between organic precursors resulting in strong, covalent bonds to afford porous, stable, and crystalline materials. COFs emerged as a field from the overarching domain of organic materials as researchers optimized both synthetic control and precursor selection. These improvements to coordination chemistry enabled non-porous and amorphous organic materials such as organic polymers to advance into the construction of porous, crystalline materials with rigid structures that granted exceptional material stability in a wide range of solvents and conditions. Through the development of reticular chemistry, precise synthetic control was achieved and resulted in ordered, nano-porous structures with highly preferential structural orientation and properties which could be synergistically enhanced and amplified. With judicious selection of COF secondary building units (SBUs), or precursors, the final structure could be predetermined, and modified with exceptional control enabling fine-tuning of emergent properties. This level of control facilitates the COF material to be designed, synthesized, and utilized in various applications, many times with metrics on scale or surpassing that of the current state-of-the-art approaches. While at University of Michigan, Omar M. Yaghi (currently at UCBerkeley) and Adrien P Cote published the first paper of COFs in 2005, reporting a series of 2D COFs. They reported the design and successful synthesis of COFs by condensation reactions of phenyl diboronic acid (C6H4[B(OH)2]2) and hexahydroxytriphenylene (C18H6(OH)6). Powder X-ray diffraction studies of the highly crystalline products having empirical formulas (C3H2BO)6·(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed 2-dimensional expanded porous graphitic layers that have either staggered conformation (COF-1) or eclipsed conformation (COF-5).
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