Post-Synthesis Amine Borane Functionalization of a Metal-Organic Framework and Its Unusual Chemical Hydrogen Release Phenomenon

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DOI

  • Samir Barman, King Abdullah University of Science and Technology, Universitat Zurich
  • ,
  • Arndt Remhof, Empa-Swiss Federal Laboratories for Materials Science and Technology
  • ,
  • Ralph Koitz, Functional Genomics Center Zürich, University of Zürich
  • ,
  • Marcella Iannuzzi, Functional Genomics Center Zürich, University of Zürich
  • ,
  • Olivier Blacque, Functional Genomics Center Zürich, University of Zürich
  • ,
  • Yigang Yan, Empa-Swiss Federal Laboratories for Materials Science and Technology
  • ,
  • Thomas Fox, Functional Genomics Center Zürich, University of Zürich
  • ,
  • Jurg Hutter, Functional Genomics Center Zürich, University of Zürich
  • ,
  • Andreas Züttel, Empa-Swiss Federal Laboratories for Materials Science and Technology, EPFL Valais Wallis
  • ,
  • Heinz Berke, Functional Genomics Center Zürich, University of Zürich

A novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation, utilizing gaseous diborane, is reported. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature, leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with a hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the mu-iminodiborane (-mu-NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H-2 liberation.

Original languageEnglish
JournalChemistry: A European Journal
Volume23
Issue37
Pages (from-to)8823-8828
Number of pages6
ISSN0947-6539
DOIs
Publication statusPublished - 3 Jul 2017

    Research areas

  • amine boranes, density functional theory, metal-organic frameworks, molecular dynamics calculations, solid state NMR spectroscopy, MAGNETIC-RESONANCE-SPECTROSCOPY, NATURAL-ABUNDANCE N-15, AMMONIA-BORANE, THERMAL-DECOMPOSITION, AMBIENT-TEMPERATURE, NMR-SPECTROSCOPY, DFT CALCULATIONS, REACTIVITY, CHEMISTRY, BORENIUM

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