Engineering Isoreticular 2D Metal-Organic Frameworks with Inherent Structural Flexibility

Alexandre Burgun, Witold M. Bloch, Christian J. Doonan, Christopher J. Sumby

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)566-575
Number of pages10
JournalAustralian Journal of Chemistry
Volume70
Issue number5
DOIs
Publication statusPublished - 2017
Externally publishedYes

Keywords

  • Isoreticulation
  • metal–organic frameworks
  • 2D networks

Fingerprint

Dive into the research topics of 'Engineering Isoreticular 2D Metal-Organic Frameworks with Inherent Structural Flexibility'. Together they form a unique fingerprint.

Cite this