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 (CH[B(OH)]) and hexahydroxytriphenylene (CH(OH)). Powder X-ray diffraction studies of the highly crystalline products having empirical formulas (CHBO)·(CH) (COF-1) and CHBO (COF-5) revealed 2-dimensional expanded porous graphitic layers that have either staggered conformation (COF-1) or eclipsed conformation (COF-5). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 Angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 to 600 °C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
The synthesis of 3D COFs has been hindered by longstanding practical and conceptual challenges until it was first achieved in 2007 by Omar M. Yaghi and colleagues, which received the Newcomb Cleveland Prize. The research team synthesized and designed the first 3D-COF ever; COF-103 and COF-108, helping unleash this new field. Unlike 0D and 1D systems, which are soluble, the insolubility of 2D and 3D structures precludes the use of stepwise synthesis, making their isolation in crystalline form very difficult. This first challenge, however, was overcome by judiciously choosing building blocks and using reversible condensation reactions to crystallize COFs.