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A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity †

1
Institute of Chemical Technology, Universität Leipzig, Linnéstr. 3, 04103 Leipzig, Germany
2
Institute of Inorganic Chemistry, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany
3
Institut für Nichtklassische Chemie e.V., Permoserstr. 15, 04318 Leipzig, Germany
*
Author to whom correspondence should be addressed.
Materials 2017, 10(4), 338; https://doi.org/10.3390/ma10040338
Received: 3 February 2017 / Revised: 16 March 2017 / Accepted: 21 March 2017 / Published: 24 March 2017
(This article belongs to the Section Porous Materials)
The synthesis and characterization of an isomorphous series of copper-containing microporous metal-organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula [Cu4(μ3-OH)2(R1-R2-trz-ia)3(H2O)x] are presented. Through size adjustment of the alkyl substituents R1 and/or R2 at the linker, the impact of linker functionalization on structure-property relationships was studied. Due to the arrangement of the substituents towards the cavities, the porosity (pore fraction 28%–39%), as well as the pore size can be adjusted by the size of the substituents of the triazole ring. Thermal analysis and temperature-dependent PXRD studies reveal a thermal stability of the MOFs up to 230 °C due to increasing framework stability through fine-tuning of the linker substitution pattern. Adsorption of CO2 (298 K) shows a decreasing maximum loading with increasing steric demand of the substituents of the triazole ring. Furthermore, the selective oxidation of cyclohexene with tert-butyl hydroperoxide (TBHP) is studied over the MOFs at 323 K in liquid chloroform. The catalytic activity increases with the steric demand of the substituents. Additionally, these isomorphous MOFs exhibit considerable robustness under oxidizing conditions confirmed by CO2 adsorption studies, as well as by the catalytic selective oxidation experiments. View Full-Text
Keywords: triazolyl isophthalate MOFs; crystal structures; structure-property relationship; linker substitution pattern; cyclohexene oxidation; heterogeneous catalysis triazolyl isophthalate MOFs; crystal structures; structure-property relationship; linker substitution pattern; cyclohexene oxidation; heterogeneous catalysis
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Junghans, U.; Kobalz, M.; Erhart, O.; Preißler, H.; Lincke, J.; Möllmer, J.; Krautscheid, H.; Gläser, R. A Series of Robust Copper-Based Triazolyl Isophthalate MOFs: Impact of Linker Functionalization on Gas Sorption and Catalytic Activity †. Materials 2017, 10, 338.

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