title: The modulator driven polymorphism of Zr(IV) based metal-organic frameworks.
abstract: The reaction of ZrCl4and 2,5-thiophenedicarboxylic acid (H2tdc) in the presence of trifluoroacetic acid (Htfa) as modulator results in the formation of the new metal-organic framework (MOF) named DUT-126 (DUT = Dresden University of Technology). The nature and concentration of modulators are found to be decisive synthetic parameters affecting the topology of the formed product. DUT-126 ( HBR: ) extends the series of polymorphs differing in topology, namely DUT-67 ( REO: ), DUT-68 ( BON: ) and DUT-69 ( BCT: ) to four, where DUT-67 and DUT-68 show the same eight-connected secondary building units as in DUT-126. In DUT-126, linker molecules have a peculiar orientation, resulting in HBR: topology, which is described for the first time in this work for MOFs. DUT-126 contains three pore types, including two micropores surrounding mesoporous channels. DUT-126 is stable against hydrolysis and features permanent porosity with a specific surface area of 1297 m2g-1and a total pore volume of 0.48 cm3g-1, calculated from the nitrogen physisorption isotherm measured at 77 K.This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.
authors.affiliation: Institute of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66, 01062 Dresden, Germany.
authors.forename: Franziska
authors.initials: F
authors.lastname: Drache
authors.affiliation: Institute of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66, 01062 Dresden, Germany.
authors.forename: Volodymyr
authors.initials: V
authors.lastname: Bon
authors.affiliation: Institute of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66, 01062 Dresden, Germany.
authors.forename: Irena
authors.identifier: http://orcid.org/0000-0001-7052-1029
authors.initials: I
authors.lastname: Senkovska
authors.affiliation: Institute of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66, 01062 Dresden, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Getzschmann
authors.affiliation: Institute of Inorganic Chemistry, Technische Universität Dresden, Bergstrasse 66, 01062 Dresden, Germany stefan.kaskel@chemie.tu-dresden.de.
authors.forename: Stefan
authors.initials: S
authors.lastname: Kaskel
keywords: 2; 5-thiophenedicarboxylic acid; metal–organic framework; polymorphism; topology; zirconium