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Flexibility and Sorption Selectivity in Rigid Metal–Organic Frameworks: The Impact of Ether-Functionalised Linkers

Authors

  • Sebastian Henke,

    1. Chair of Inorganic Chemistry II, Organometallics and Materials Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany), Fax: (+49) 234-32-14174
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  • Dr. Rochus Schmid,

    1. Chair of Inorganic Chemistry II, Organometallics and Materials Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany), Fax: (+49) 234-32-14174
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  • Prof. Dr. Jan-Dierk Grunwaldt,

    1. Chair for Chemical Technology and Catalysis, Institute for Technical Chemistry and Polymer Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 20, 76131 Karlsruhe (Germany)
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  • Prof. Dr. Roland A. Fischer

    Corresponding author
    1. Chair of Inorganic Chemistry II, Organometallics and Materials Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany), Fax: (+49) 234-32-14174
    • Chair of Inorganic Chemistry II, Organometallics and Materials Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum (Germany), Fax: (+49) 234-32-14174
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Abstract

The functionalisation of well-known rigid metal–organic frameworks (namely, [Zn4O(bdc)3]n, MOF-5, IRMOF-1 and [Zn2(bdc)2(dabco)]n; bdc=1,4-benzene dicarboxylate, dabco=diazabicyclo[2.2.2]octane) with additional alkyl ether groups of the type -O-(CH2)n-O-CH3 (n = 2–4) initiates unexpected structural flexibility, as well as high sorption selectivity towards CO2 over N2 and CH4 in the porous materials. These novel materials respond to the presence/absence of guest molecules with structural transformations. We found that the chain length of the alkyl ether groups and the substitution pattern of the bdc-type linker have a major impact on structural flexibility and sorption selectivity. Remarkably, our results show that a high crystalline order of the activated material is not a prerequisite to achieve significant porosity and high sorption selectivity.

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