Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon
Online Publication Date2017-06-13
Print Publication Date2017-07-03
Permanent link to this recordhttp://hdl.handle.net/10754/623681
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AbstractWe report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. 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 hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the -iminodiborane ((--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 H2 liberation.
CitationBerke H, Barman S, Remhof A, Koitz R, Iannuzzi M, et al. (2017) Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon. Chemistry - A European Journal. Available: http://dx.doi.org/10.1002/chem.201702013.
SponsorsFunding from the Swiss National Science Foundation (SNSF), University of Zurich and generous computing resources from the University of Zurich are gratefully acknowledged.
JournalChemistry - A European Journal
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Barman, S., Remhof, A., Koitz, R., Iannuzzi, M., Blacque, O., Yan, Y., Fox, T., Hutter, J., Züttel, A., & Berke, H. (2017). CCDC 858960: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CCXTTDX. DOI: 10.5517/ccdc.csd.ccxttdx Handle: 10754/663858