Structural dynamics inside a functionalized metal-organic framework probed by ultrafast 2D IR spectroscopy
2014 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 111, no 52, 18442-18447 p.Article in journal (Refereed) Published
The structural elasticity of metal-organic frameworks (MOFs) is a key property for their functionality. Here, 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. Methodology advances were required to remove the severe light scattering caused by the macroscopic-sizedMOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Forster vibrational excitation transfer.
Place, publisher, year, edition, pages
2014. Vol. 111, no 52, 18442-18447 p.
2D IR spectroscopy, metal-organic framework, UiO-66 MOF, ultrafast structural fluctuations, solvent confinement effect
IdentifiersURN: urn:nbn:se:uu:diva-243676DOI: 10.1073/pnas.1422194112ISI: 000347444400026PubMedID: 25512539OAI: oai:DiVA.org:uu-243676DiVA: diva2:789689