Non-interpenetrated metal-organic frameworks based on copper(II) paddlewheel and oligoparaxylene-isophthalate linkers: synthesis, structure and gas adsorption

Yan, Yong and Juricek, Michal and Coudert, Francois-Xavier and Vermeulan, Nicolaas A. and Grunder, Sergio and Dailly, Anne and Lewis, William and Blake, Alexander J. and Stoddart, J. Fraser and Schröder, Martin (2016) Non-interpenetrated metal-organic frameworks based on copper(II) paddlewheel and oligoparaxylene-isophthalate linkers: synthesis, structure and gas adsorption. Journal of the American Chemical Society, 138 (10). pp. 3371-3381. ISSN 1520-5126

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Abstract

Two metal–organic framework materials, MFM-130 and MFM-131 (MFM = Manchester Framework Material), have been synthesized using two oligoparaxylene (OPX) tetracarboxylate linkers containing four and five aromatic rings, respectively. Both fof-type non-interpenetrated networks contain Kagomé lattice layers comprising [Cu2(COO)4] paddlewheel units and isophthalates, which are pillared by the OPX linkers. Desolvated MFM-130, MFM-130a, shows permanent porosity (BET surface area of 2173 m2/g, pore volume of 1.0 cm3/g), high H2 storage capacity at 77 K (5.3 wt% at 20 bar and 2.2 wt% at 1 bar), and a higher CH4 adsorption uptake (163 cm3(STP)/cm3 (35 bar and 298 K)) compared with its structural analogue, NOTT-103. MFM-130a also shows impressive selective adsorption of C2H2, C2H4, and C2H6 over CH4 at room temperature, indicating its potential for separation of C2 hydrocarbons from CH4. The single-crystal structure of MFM-131 confirms that the methyl substituents of the paraxylene units block the windows in the Kagomé lattice layer of the framework, effectively inhibiting network interpenetration in MFM-131. This situation is to be contrasted with that of the doubly interpenetrated oligophenylene analogue, NOTT-104. Calculation of the mechanical properties of these two MOFs confirms and explains the instability of MFM-131 upon desolvation in contrast to the behavior of MFM-130. The incorporation of paraxylene units, therefore, provides an efficient method for preventing network interpenetration as well as accessing new functional materials with modified and selective sorption properties for gas substrates.

Item Type: Article
Keywords: metal-organic framework, Shear modulus, copper, methane, hydrogen, hydrocarbon, gas storage
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1021/jacs.5b12312
Depositing User: Bramwell, Roseanna
Date Deposited: 21 Mar 2016 11:48
Last Modified: 15 Sep 2016 00:17
URI: http://eprints.nottingham.ac.uk/id/eprint/32412

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