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Size-Selective Urea-Containing Metal-Organic Frameworks as Receptors for Anions.

Leili Esrafili1, Ali Morsali1, Mao-Lin Hu2

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Inorganic Chemistry
|October 29, 2020
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Summary

New metal-organic frameworks (MOFs) with urea groups show promise for detecting specific anions in water. These MOFs, TMU-67 and TMU-68, exhibit selectivity for dihydrogen arsenate and fluoride, respectively, overcoming challenges in anion recognition.

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science
  • Coordination Chemistry

Background:

  • Anion recognition in aqueous solutions using neutral hosts is a significant challenge in supramolecular chemistry.
  • Urea derivatives are effective neutral anion receptors but suffer from detrimental self-association.
  • Immobilizing urea onto rigid metal-organic frameworks (MOFs) can prevent self-association and enhance recognition.

Purpose of the Study:

  • To synthesize and characterize novel urea-containing MOFs for anion recognition in water.
  • To evaluate the anion binding affinity and selectivity of the synthesized MOFs.
  • To elucidate the structural basis for the observed anion sensing capabilities.

Main Methods:

  • Synthesis of two new urea-functionalized MOFs: TMU-67 and TMU-68.
  • Assessment of anion recognition abilities in aqueous media.
  • Crystal structure characterization to analyze network topology and hydrogen bonding interactions.

Main Results:

  • TMU-67 and TMU-68 exhibit good water stability and anion affinity.
  • TMU-67 shows selectivity for dihydrogen arsenate, while TMU-68 is selective for fluoride.
  • Network interpenetration in both MOFs shapes voids, creating selective sites for anion binding, despite urea N-H bonds being involved in framework interactions.

Conclusions:

  • Urea-containing MOFs can be effectively designed for selective anion recognition in water.
  • Network interpenetration plays a crucial role in creating selective binding environments within the MOFs.
  • TMU-67 and TMU-68 represent promising materials for sensing specific anions like arsenate and fluoride.