Multivariate Hydrogen-Bonded Organic Frameworks with Tunable Permanent Porosities for Capture of a Mustard Gas Simulant |
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Authors: | Xiang Yu Gao Yao Wang Enyu Wu Chen Wang Bin Li Prof. Dr. Yaming Zhou Banglin Chen Dr. Peng Li |
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Affiliation: | 1. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438 China These authors contributed equally to this work.;2. State Key Laboratory of Silicon Materials, School of Materials Science and Engineering, Zhejiang University, Hang-zhou, 310027 China;3. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan University, 2005 Songhu Road, Shanghai, 200438 China;4. Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry & Materials Science, Fujian Normal University, Fuzhou, Fujian, 350000 China |
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Abstract: | Precise synthesis of topologically predictable and discrete molecular crystals with permanent porosities remains a long-term challenge. Here, we report the first successful synthesis of a series of 11 isoreticular multivariate hydrogen-bonded organic frameworks (MTV-HOFs) from pyrene-based derivatives bearing −H, −CH3, −NH2 and −F groups achieved by a shape-fitted, π–π stacking self-assembly strategy. These MTV-HOFs are single-crystalline materials composed of tecton, as verified by single-crystal diffraction, nuclear magnetic resonance (NMR) spectra, Raman spectra, water sorption isotherms and density functional theory (DFT) calculations. These MTV-HOFs exhibit tunable hydrophobicity with water uptake starting from 50 to 80 % relative humidity, by adjusting the combinations and ratios of functional groups. As a proof of application, the resulting MTV-HOFs were shown to be capable of capturing a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES) from moisture. The location of different functional groups within the pores of the MTV-HOFs leads to a synergistic effect, which resulted in a superior CEES/H2O selectivity (up to 94 %) compared to that of the HOFs with only pure component and enhanced breakthrough performance (up to 4000 min/g) when compared to benchmark MOF materials. This work is an important advance in the synthesis of MTV-HOFs, and provides a platform for the development of porous molecular materials for numerous applications. |
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Keywords: | Hydrogen-Bonded Organic Frameworks Porous Molecular Materials Selective Gas Separation |
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