Paddle Wheel Based Triazolyl Isophthalate MOFs: Impact of Linker Modification on Crystal Structure and Gas Sorption Properties

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• 作者：Merten Kobalz ; Jörg Lincke ; Karolin Kobalz ; Oliver Erhart ; Jens Bergmann ; Daniel Lässig ; Marcus Lange ; Jens Möllmer ; Roger Gläser ; Reiner Staudt ; Harald Krautscheid
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：March 21, 2016
• 年：2016
• 卷：55
• 期：6
• 页码：3030-3039
• 全文大小：743K
• ISSN：1520-510X

文摘

Syntheses and comprehensive characterization of two closely related series of isomorphous metal–organic frameworks (MOFs) based on triazolyl isophthalate linkers with the general formula _∞³[M₂(R¹–R²–trz–ia)₂] (M = Cu, Zn) are presented. Using solvothermal synthesis and synthesis of microcrystalline materials on the gram scale by refluxing a solution of the starting materials, 11 MOFs are readily available for a systematic investigation of structure–property relationships. The networks of the two series are assigned to rutile (rtl) (1–4) and α-PbO₂ (apo) (5–9) topology, respectively. Due to the orientation of the triazole substituents toward the cavities, both the pore volume and the pore diameter can be adjusted by choice of the alkyl substituents. Compounds 1–9 exhibit pronounced microporosity with calculated porosities of 31–53% and show thermal stability up to 390 °C as confirmed by simultaneous thermal analysis. Systematic investigation of adsorption properties by CO₂ (298 K) and N₂ (77 K) adsorption studies reveal remarkable network flexibility induced by alkyl substituents on the linker. Fine-tuning of the gate opening pressure and of the hysteresis shape is possible by adjusting the substitution pattern and by choice of the metal ion.