Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers

Dongyang Zhu, Yifan Zhu, Yu Chen, Qianqian Yan, Han Wu, Chun-Yen Liu, Xu Wang, Lawrence B. Alemany, Guanhui Gao, Thomas P. Senftle, Yongwu Peng, Xiaowei Wu () and Rafael Verduzco ()
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Dongyang Zhu: Rice University
Yifan Zhu: Rice University
Yu Chen: Rice University
Qianqian Yan: Rice University
Han Wu: Ganjiang Chinese Medicine Innovation Center
Chun-Yen Liu: Rice University
Xu Wang: Rice University
Lawrence B. Alemany: Rice University
Guanhui Gao: Rice University
Thomas P. Senftle: Rice University
Yongwu Peng: Zhejiang University of Technology
Xiaowei Wu: Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials, Xiamen Institute of Rare Earth Materials, Fujian Institute of Research on the Structure of Matter, Haixi Institutes, Chinese Academy of Sciences
Rafael Verduzco: Rice University

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental and practical point of view. However, the construction of highly crystalline 3D COF remains challenging. At the same time, the choice of topologies in 3D COFs is limited by the crystallization problem, the lack of availability of suitable building blocks with appropriate reactivity and symmetries, and the difficulties in crystalline structure determination. Herein, we report two highly crystalline 3D COFs with pto and mhq-z topologies designed by rationally selecting rectangular-planar and trigonal-planar building blocks with appropriate conformational strains. The pto 3D COFs show a large pore size of 46 Å with an extremely low calculated density. The mhq-z net topology is solely constructed from totally face-enclosed organic polyhedra displaying a precise uniform micropore size of 1.0 nm. The 3D COFs show a high CO2 adsorption capacity at room temperature and can potentially serve as promising carbon capture adsorbents. This work expands the choice of accessible 3D COF topologies, enriching the structural versatility of COFs.

Date: 2023
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DOI: 10.1038/s41467-023-38538-x

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