The Anisotropic Responses of a Flexible Metal-Organic Framework Constructed from Asymmetric Flexible Linkers and Heptanuclear Zinc Carboxylate Secondary Building Units


Carrington, Elliot J ORCID: 0000-0001-8855-809X, Petuya, Remi ORCID: 0000-0002-3118-6966, Hylton, Rebecca K, Yan, Yong, Antypov, Dmytro ORCID: 0000-0003-1893-7785, Darling, George R ORCID: 0000-0001-9329-9993, Dyer, Matthew S ORCID: 0000-0002-4923-3003, Berry, Neil G ORCID: 0000-0003-1928-0738, Katsoulidis, Alexandros P ORCID: 0000-0003-0860-7440 and Rosseinsky, Matthew J ORCID: 0000-0002-1910-2483 (2019) The Anisotropic Responses of a Flexible Metal-Organic Framework Constructed from Asymmetric Flexible Linkers and Heptanuclear Zinc Carboxylate Secondary Building Units. CRYSTAL GROWTH & DESIGN, 19 (10). pp. 5604-5618.

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Abstract

A new porous and flexible metal-organic framework (MOF) has been synthesized from the flexible asymmetric linker <i>N</i>-(4-carboxyphenyl)succinamate (CSA) and heptanuclear zinc oxo-clusters of formula [Zn<sub>7</sub>O<sub>2</sub>(carboxylate)<sub>10</sub>DMF<sub>2</sub>] involving two coordinated terminal DMF ligands. The structural response of this MOF to the removal or exchange of its guest molecules has been probed using a combination of experimental and computational approaches. The topology of the material, involving double linker connections in the <i>a</i> and <i>b</i> directions and single linker connections along the <i>c</i> axis, is shown to be key in the material's anisotropic response. The <i>a</i> and <i>b</i> directions remain locked during guest removal, whereas the <i>c</i> axis linker undergoes large changes significantly reducing the material's void space. The changes to the <i>c</i> axis linker involve a combination of a hinge motion on the linker's rigid side and conformational rearrangements on its flexible end, which were probed in detail during this process despite the presence of crystallographic disorder along this axis, which prevented accurate characterization by experimental methods alone. Although inactive during guest removal, the flexible ends of the <i>a</i> and <i>b</i> axis linkers are observed to play a prominent role during DMF to DMSO solvent exchange, facilitating the exchange reaction arising in the cluster.

Item Type: Article
Uncontrolled Keywords: Prevention
Depositing User: Symplectic Admin
Date Deposited: 22 Aug 2019 09:54
Last Modified: 14 Mar 2024 19:05
DOI: 10.1021/acs.cgd.9b00558
Open Access URL: https://pubs.acs.org/doi/pdf/10.1021/acs.cgd.9b005...
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URI: https://livrepository.liverpool.ac.uk/id/eprint/3052311
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