Controllable Synthesis and Performance Modulation of 2D Covalent-Organic Frameworks.

Covalent-organic frameworks (COFs) are especially interesting and unique as their highly ordered topological structures entirely built from plentiful π-conjugated units through covalent bonds. Arranging tailorable organic building blocks into periodically reticular skeleton bestows predictable lattices and various properties upon COFs in respect of topology diagrams, pore size, properties of channel wall interfaces, etc. Indeed, these peculiar features in terms of crystallinity, conjugation degree, and topology diagrams fundamentally decide the applications of COFs including heterogeneous catalysis, energy conversion, proton conduction, light emission, and optoelectronic devices. Additionally, this research field has attracted widespread attention and is of importance with a major breakthrough in recent year. However, this research field is running with the lack of summaries about tailorable construction of 2D COFs for targeted functionalities. This review first covers some crucial polymeric strategies of preparing COFs, containing boron ester condensation, amine-aldehyde condensation, Knoevenagel condensation, trimerization reaction, Suzuki CC coupling reaction, and hybrid polycondensation. Subsequently, a summary is made of some representative building blocks, and then underlines how the electronic and molecular structures of building blocks can strongly influence the functional performance of COFs. Finally, conclusion and perspectives on 2D COFs for further study are proposed.