title: Flexibility and sorption selectivity in rigid metal-organic frameworks: the impact of ether-functionalised linkers.
abstract: The functionalisation of well-known rigid metal-organic frameworks (namely, [Zn(4)O(bdc)(3)](n), MOF-5, IRMOF-1 and [Zn(2)(bdc)(2)(dabco)](n); bdc = 1,4-benzene dicarboxylate, dabco = diazabicyclo[2.2.2]octane) with additional alkyl ether groups of the type -O-(CH(2))(n)-O-CH(3) (n = 2-4) initiates unexpected structural flexibility, as well as high sorption selectivity towards CO(2) over N(2) and CH(4) 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.
authors.affiliation: Organometallics and Materials Chemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780 Bochum, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Henke
authors.forename: Rochus
authors.initials: R
authors.lastname: Schmid
authors.forename: Jan-Dierk
authors.initials: JD
authors.lastname: Grunwaldt
authors.forename: Roland A
authors.initials: RA
authors.lastname: Fischer
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D016062:Porosity; D015032:Zinc / Q000737:chemistry*
chemical_list: D001555:Benzene Derivatives; D009942:Organometallic Compounds; C512711:zinc benzenedicarboxylate; D002245:Carbon Dioxide; D015032:Zinc