• Yuri A. Mezenov
  • Stephanie Bruyere
  • Andrei Krasilin
  • Ekaterina Khrapova
  • Semyon V. Bachinin
  • Pavel V. Alekseevskiy
  • Sergei Shipiloskikh
  • Pascal Boulet
  • Sebastien Hupont
  • Alexandre Nomine
  • Brigitte Vigolo
  • Alexander S. Novikov
  • Thierry Belmonte
  • Valentin A. Milichko

Metal-organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M-BTC (M: Fe3+, Co3+, Co2+, Ni2+, and Cu2+ BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.

Original languageEnglish
Pages (from-to)13992–14003
Number of pages12
JournalInorganic Chemistry
Volume61
Issue number35
DOIs
StatePublished - 5 Sep 2022

    Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

ID: 98879365