Probing the Dynamics of the Porous Zr Terephthalate UiO-66 Framework Using <sup>2</sup>H NMR and Neutron Scattering

Kolokolov, Daniil I.; Stepanov, Alexander G.; Guillerm, Vincent; Serre, Christian; Frick, B.; Jobic, H.

doi:10.1021/jp3029193

Cited by 102 publications

(134 citation statements)

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“…The functionalized UiO-66 MOFs were prepared by postsynthetic exchange of the ligand component of the framework (4). UiO-66 was immersed in an aqueous solution of [FeFe](dcbdt)(CO) 6 at room temperature for 24 h. A schematic illustration of the MOF with a functionalized linker is shown in Fig. 1A.…”

Section: Resultsmentioning

confidence: 99%

“…The loading of the functional group can be varied by changing the ratio of UiO-66 to [FeFe](dcbdt)(CO) 6 during the postsynthetic exchange reaction. Samples with the loadings of 14%, 2.5 ± 1.1%, and 0.2 ± 0.1% were prepared, where the loadings are expressed as the percentage of incorporated [FeFe](dcbdt)(CO) 6 compared with the total number of all linkers (Fig. S1 A-C).…”

Section: Resultsmentioning

confidence: 99%

“…The relatively slow motions of the framework occurring in submicrosecond to millisecond scales have been studied by NMR and neutron scattering (6). However, until now, quantitative measurements that can characterize the time dependence of MOF structural motions in ultrafast regimes have not been possible because of the lack of appropriate techniques.…”

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confidence: 99%

“…Recently, Pullen et al (4) showed that a di-iron carbonyl complex [FeFe](dcbdt)(CO) 6 (dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) can be incorporated into UiO-66 zirconium MOF as a linker in the framework (Fig. 1) (4).…”

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confidence: 99%

“…S8). In addition, the analog of the vibrational probe that is lacking the carboxylate groups, [FeFe](bdt)(CO) 6 (bdt = benzene-1,2-dithiolate), was dissolved in bulk DMF as a 3.3 mM solution, and the CLS decay was measured in the same manner as used for the MOF samples. The dynamical parameters extracted from the CLS decays are given in Table 2.…”

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

Nishida

Tamimi

Fei

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

108

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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-sized MOF particles, eliminate interfering oscillatory components from the 2D IR data, and address Förster vibrational excitation transfer.2D IR spectroscopy | metal-organic framework | UiO-66 MOF | ultrafast structural fluctuations | solvent confinement effect M etal-organic frameworks (MOFs) are molecular architectures in which metal clusters are connected by organic linkers to yield relatively regular 3D coordination polymers with nanometer-sized pores (1, 2). MOFs have been investigated for a wide variety of chemical applications, such as adsorption of gases (3) and heterogeneous catalysts (4). Among many types of porous materials, MOFs are unique because of their structural elasticity coexisting with a high degree of spatial regularity. In some sense, MOFs are like crystals and polymers. They have relatively regular structures like a crystal, but the metal clusters are joined by organic linkers that, in some systems, produce significant structural mobility. The elasticity of MOFs is intimately related to their physical properties and behavior (5).An important goal for understanding the nature of MOFs and how their chemical composition influences their properties and applications is to develop and apply an experimental method that can measure the ultrafast structural motions of MOFs. The relatively slow motions of the framework occurring in submicrosecond to millisecond scales have been studied by NMR and neutron scattering (6). However, until now, quantitative measurements that can characterize the time dependence of MOF structural motions in ultrafast regimes have not been possible because of the lack of appropriate techniques. Here, we have accomplished the goal by applying ultrafast 2D IR spectroscopy (7) to the study of MOF structural dynamics. 2D IR is akin to 2D NMR, but it operates on the ultrafast timescales necessary to characterize the time dependence of MOF structural motions. In addition, there is the important question of the effects on MOF dynamics when guest molecules fill the MOF nanopores. The guest molecules will affect the structural fluctuations of the framework by interacting with the linkers and the metal units. Furthermore, because of the confinement of guest molecules in MOF nanopores, the dynamics of these molecules are expected to be very different from t...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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confidence: 99%

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