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Title: Structural dynamics inside a functionalized metal–organic framework probed by ultrafast 2D IR spectroscopy

One key property of metal-organic frameworks (MOFs) are their structural elasticity. IHere we show that 2D IR spectroscopy with pulse-shaping techniques can probe the ultrafast structural fluctuations of MOFs. 2D IR data, obtained from a vibrational probe attached to the linkers of UiO-66 MOF in low concentration, revealed that the structural fluctuations have time constants of 7 and 670 ps with no solvent. Filling the MOF pores with dimethylformamide (DMF) slows the structural fluctuations by reducing the ability of the MOF to undergo deformations, and the dynamics of the DMF molecules are also greatly restricted. Finally, methodology advances were required to remove the severe light scattering caused by the macroscopic-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer.
 [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [2] ;  [1]
  1. Stanford Univ., CA (United States). Dept. of Chemistry
  2. Univ. of California, San Diego, CA (United States). Dept. of Chemistry and Biochemistry
  3. Uppsala Univ. (Sweden). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 111; Journal Issue: 52; Journal ID: ISSN 0027-8424
National Academy of Sciences, Washington, DC (United States)
Research Org:
Stanford Univ., CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 2D IR spectroscopy; metal–organic framework; UiO-66 MOF; ultrafast structural fluctuations; solvent confinement effect
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1347956