Direct Probing of Vibrational Interactions in UiO-66 Polycrystalline Membranes with Femtosecond Two-Dimensional Infrared Spectroscopy

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DOI http://dx.doi.org/10.1021/acs.jpclett.2c02509
Reference A.A. Korotkevich, O.O. Sofronov, O. Lugier, S. Sengupta, S. Tanase and H.J. Bakker, Direct Probing of Vibrational Interactions in UiO-66 Polycrystalline Membranes with Femtosecond Two-Dimensional Infrared Spectroscopy, J. Phys. Chem. Lett. 13, 9793-9800 (2022)
Group Ultrafast Spectroscopy

UiO-66 is a benchmark metal–organic framework that holds great promise for the design of new functional materials. In this work, we perform two-dimensional infrared measurements on polycrystalline membranes of UiO-66 grown on c-sapphire substrates. We study the symmetric and antisymmetric stretch vibrations of the carboxylate groups of the terephthalate linker ions and find that these vibrations show a rapid energy exchange and a collective vibrational relaxation with a time constant of 1.3 ps. We also find that the symmetric vibration of the carboxylate group is strongly coupled to a vibration of the aromatic ring of the terephthalate ion. We observe that the antisymmetric carboxylate vibrations of different terephthalate linkers show rapid resonant (Förster) energy transfer with a time constant of ∼1 ps.