Covalent Organic Frameworks with Record Pore Apertures

The pore apertures dictate the guest accessibilities of the pores, imparting diverse functions to porous materials. It is highly desired to construct crystalline porous polymers with predesignable and uniform mesopores that can allow large organic, inorganic, and biological molecules to enter. However, due to the ease of the formation of interpenetrated and/or fragile structures, the largest pore aperture reported in the metal-organic frameworks is 8.5 nm, and the value for covalent organic frameworks (COFs) is only 5.8 nm. Herein, we construct a series of COFs with record pore aperture values from 7.7 to 10.0 nm by designing building blocks with large conformational rigidness, planarity, and suitable local polarity. All of the obtained COFs possess eclipsed stacking structures, high crystallinity, permanent porosity, and high stability. As a proof of concept, we successfully employed these COFs to separate pepsin that is ∼7 nm in size from its crudes and to protect tyrosinase from heat-induced deactivation.