2.5-dimensional covalent organic frameworks

Abstract Covalently bonded crystalline substances with micropores have broad applications. Covalent organic frameworks (COFs) are representative of such substances. They have so far been classified into two-dimensional (2D) and three-dimensional (3D) COFs. 2D-COFs have planar shapes useful for broad purposes, but obtaining good crystals of 2D-COFs with sizes larger than 10 μm is significantly challenging, whereas yielding 3D-COFs with high crystallinity and larger sizes is easier. Here, we show COFs with 2.5-dimensional (2.5D) skeletons, which are microscopically constructed with 3D bonds but have macroscopically 2D planar shapes. The 2.5D-COFs shown herein achieve large single-crystal sizes above 0.1 mm and ultrahigh-density primary amines regularly allocated on and pointing perpendicular to the covalently-bonded network plane. Owing to the latter nature, the COFs are promising as CO 2 adsorbents that can simultaneously achieve high CO 2 /N 2 selectivity and low heat of adsorption, which are usually in a mutually exclusive relationship. 2.5D-COFs are expected to broaden the frontier and application of covalently bonded microporous crystalline systems.