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Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks

Abstract

The structure-property relationship investigation is of prime importance to development of porous MOFs possessing better performance. In this work, two regioisomeric diisophthalate ligands, with the only difference being the position of methyl and amine groups with respect to isophthalate moieties, were rationally designed and synthesized, and their corresponding dicopper paddlewheel-based MOFs were successfully fabricated under suitable solvothermal conditions. Single-crystal X-ray diffraction studies showed that they displayed the same network topology of ssa type, thus providing a platform to investigate the impact of the substituent’s arrangement on gas adsorption properties. As revealed by gas adsorption studies, the pore textural properties and gas uptake capacities with respect to C2H2, CO2, and CH4 of ZJNU-11 are significantly higher than those of its isomer ZJNU-12 despite their same structures, indicating that the arrangement of functional groups makes a difference to the framework stabilities against desolvation and thus gas adsorption properties. In addition, ZJNU-11 is also capable of selectively adsorptive separation of C2H2 and CO2 from CH4, with high C2H2/CH4 (v/v, 1/1) and CO2/CH4 (v/v, 1/1) adsorption selectivities of 36.2 and 5.9 at 298 K and 1 atm. This work not only reported a porous MOF material for highly selective C2H2/CH4 and CO2/CH4 separations, but also demonstrated that the rational arrangement of substituent groups will be favorable to improve the MOF’s stabilities and thus gas adsorption properties, which needs to be taken into account upon design and construction of porous MOFs.

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Supplementary files

Publication details

The article was received on 08 Jun 2019, accepted on 10 Jul 2019 and first published on 10 Jul 2019


Article type: Paper
DOI: 10.1039/C9CE00882A
CrystEngComm, 2019, Accepted Manuscript

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    Effect of arrangement of functional groups on stability and gas adsorption properties in two regioisomeric copper bent diisophthalate frameworks

    T. Xu, Z. Jiang, M. He, X. Gao and Y. He, CrystEngComm, 2019, Accepted Manuscript , DOI: 10.1039/C9CE00882A

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