Photoswitchable Radical State in Nanoporous Metal–Organic Framework Films with Embedded Hexaarylbiimidazole

  • chair:

    Liu, Y. / Jiang, Y. / Heinke, L. (2024)

  • place:

    Langmuir 2024, 40, 1, 474–479

  • Date: Januar 2024
  • Abstract

    Photoresponsive materials enable dynamic remote control of their fundamental properties. The incorporation of photochromic molecules in nanoporous metal–organic frameworks (MOFs) provides a unique opportunity to tailor the material properties, including the interaction between the MOF host and guest molecules in the pores. Here, a MOF film of type HKUST-1 with embedded hexaarylbiimidazole (HABI), undergoing reversible light-induced reactions between the stable dimer state and the metastable radical state, is presented. The switching between the dimer and radical form is shown by infrared, UV–vis, and electron paramagnetic resonance (EPR) spectroscopy. By transient uptake experiments with ethanol and methanol as probe molecules, we show that the dimer-radical switching impacts the host–guest interaction and, in particular, modifies the uptake amount and diffusion coefficient of the guest molecules. For ethanol, the diffusion slows down by 75%. This research presents the first MOF material with photoswitchable (meta)stable dimer and radical molecules, and it contributes to the advancement of photoresponsive nanoporous materials.