Please use this identifier to cite or link to this item: http://hdl.handle.net/2440/106166
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Type: Journal article
Title: Engineering isoreticular 2D metal-organic frameworks with inherent structural flexibility
Author: Burgun, A.
Bloch, W.
Doonan, C.
Sumby, C.
Citation: Australian Journal of Chemistry, 2017; 70(5):566-575
Publisher: CSIRO Publishing
Issue Date: 2017
ISSN: 0004-9425
1445-0038
Statement of
Responsibility: 
Alexandre Burgun, Witold M. Bloch, Christian J. Doonan and Christopher J. Sumby
Abstract: The chemical mutability of metal–organic frameworks (MOFs) is an advantageous feature that allows fine-tuning of their physical and chemical properties. Herein, we report the successful isoreticulation of a MOF with an outstanding gas selectivity for CO2 versus N2: [Cu(L1)(H2O)]·xS (CuL1), where H2L1 = bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane) and S = solvate. By modifying the steric bulk and length of the original ligand, we synthesised three new MOFs with 2D networks isoreticular to CuL1, namely [Cu(L1Me)(H2O)]·xS (CuL1Me), [Cu(L2)(H2O)]·xS (CuL2), and [Cu(L2Me)(H2O)]·xS (CuL2Me) (where H2L1Me = bis(4-(4-carboxyphenyl)-3,5-dimethyl-1H-pyrazolyl)methane, H2L2 = bis(4-(4-carboxyphenyl)-(ethyne-2,1-yl)-1H-pyrazolyl)methane, and H2L2Me = bis(4-(4-carboxyphenyl)-(ethyne-2,1-yl)-3,5-dimethyl-1H-pyrazolyl)methane). Depending on the steric hindrance and structure metrics of the organic links, staggered and eclipsed arrangements of 2D 44 net layers were obtained. The anisotropy of the pore dimensions is proportional to the linker length (L2 and L2Me), which when increased, renders these materials non-porous. However, the more sterically demanding ligand L1Me gives a material that shows gate-opening behaviour in response to a CO2 absorbate. The synthesis and structure of an unexpected mixed-valence CuII/CuI 3D MOF, Cu3[Cu(L2Me)2]2(H2O)4]·xS (Cu5(L2Me)4), containing an unusual trimeric CuII node are also reported.
Rights: Journal compilation © CSIRO 2017
RMID: 0030070094
DOI: 10.1071/CH16663
Appears in Collections:Chemical Engineering publications

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