2.5-dimensional covalent organic frameworks

Tomoki Kitano, Syunto Goto, Xiaohan Wang, Takayuki Kamihara, Yoshihisa Sei, Yukihito Kondo, Takumi Sannomiya, Hidehiro Uekusa and Yoichi Murakami ()
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Tomoki Kitano: Institute of Science Tokyo
Syunto Goto: Institute of Science Tokyo
Xiaohan Wang: Institute of Science Tokyo
Takayuki Kamihara: Institute of Science Tokyo
Yoshihisa Sei: Institute of Science Tokyo
Yukihito Kondo: Institute of Science Tokyo
Takumi Sannomiya: Institute of Science Tokyo
Hidehiro Uekusa: Institute of Science Tokyo
Yoichi Murakami: Institute of Science Tokyo

Nature Communications, 2025, vol. 16, issue 1, 1-10

Abstract: 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 CO2 adsorbents that can simultaneously achieve high CO2/N2 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.

Date: 2025
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DOI: 10.1038/s41467-024-55729-2

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