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Framework interpenetration in metal-organic frameworks (MOFs) can enhance ion-sensing. A small ligand change created two MOFs with different interpenetration, leading to selective fluorescence quenching for detecting metal ions like gold.

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Area of Science:

  • Materials Science
  • Coordination Chemistry
  • Supramolecular Chemistry

Background:

  • Framework interpenetration in metal-organic frameworks (MOFs) is typically viewed as detrimental to porosity.
  • However, interpenetration can also stabilize framework structures and create unique microenvironments.
  • These confined spaces can influence guest molecule interactions and photophysical properties.

Purpose of the Study:

  • To investigate how subtle changes in ligand structure affect framework interpenetration in a unified Zn(II) platform.
  • To explore the relationship between interpenetration degree, cluster coordination, and ion-sensing capabilities.
  • To establish structure-property correlations for guest-responsive photophysics in MOFs.

Main Methods:

  • Synthesis of two topologically identical Zn(II)-based MOFs using fluorene-based dipyridyl ligands with varying steric bulk.
  • Single-crystal X-ray diffraction analysis to determine framework structures and interpenetration degrees.
  • Fluorescence spectroscopy to evaluate ion-sensing performance in aqueous media.

Main Results:

  • Two MOFs, [Zn4(L1)4(L2)2]n (1) and [Zn4(L1)4(L3)2]n (2), were synthesized with 3-fold and 4-fold interpenetration, respectively.
  • MOF 1 exhibited fully coordinated paddlewheel clusters, while MOF 2 featured partially coordinated clusters with accessible sites.
  • MOF 1 selectively detected Au3+ with a low detection limit (0.99 μM) via fluorescence quenching.
  • MOF 2 detected Au3+, Ag+, and Cu2+ with detection limits ranging from 2.15 to 2.51 μM.

Conclusions:

  • Subtle steric modifications in ligands can precisely control the degree of framework interpenetration in MOFs.
  • The saturation of metal clusters and the presence of open coordination sites are directly linked to interpenetration.
  • These structural features dictate the selective fluorescence quenching behavior for different metal ions, highlighting a tunable platform for ion sensing.