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

摘要

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)(infinity)[M-2(R-1-R-2-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 alpha-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 degrees C as confirmed by simultaneous thermal analysis. Systematic investigation of adsorption properties by CO2 (298 K) and N-2 (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.