Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR

He, Peng; Lucier, Bryan E. G.; Terskikh, Victor V.; Shi, Qi; Dong, Jinxiang; Chu, Y. P.; Zheng, Anmin; Sutrisno, Andre; Huang, Yining

doi:10.1021/jp5063868

Cited by 59 publications

(53 citation statements)

References 93 publications

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“…Nowadays, the use of high‐field NMR spectrometers facilitates the SSNMR detection of metal centers in MOFs and zeolites . Huang's group has performed a series of studies on metal centers in MOFs using a 21.1 T high‐field SSNMR spectrometer . They applied 25 Mg NMR to study the local binding environment of magnesium centers in MOFs .…”

Section: Interfaces In Nanoporous Materialsmentioning

confidence: 99%

“…The authors also observed distinct spectroscopic features resulting from adsorbed benzene or dimethylformamide. In their work published in 2014, SSNMR experiments were conducted on a series of “uncommon” quadrupolar nuclei including 49 Ti, 67 Zn, 91 Zr, 115 In, and 139 La. The interpretation of the SSNMR data opened new access to the subtle differences in coordination, bond‐length distribution, and ligand geometry about the metal centers in different MOF materials.…”

Section: Interfaces In Nanoporous Materialsmentioning

confidence: 99%

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Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid‐State NMR

et al. 2017

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Surface and interfacial chemistry is of fundamental importance in functional nanomaterials applied in catalysis, energy storage and conversion, medicine, and other nanotechnologies. It has been a perpetual challenge for the scientific community to get an accurate and comprehensive picture of the structures, dynamics, and interactions at interfaces. Here, some recent examples in the major disciplines of nanomaterials are selected (e.g., nanoporous materials, battery materials, nanocrystals and quantum dots, supramolecular assemblies, drug-delivery systems, ionomers, and graphite oxides) and it is shown how interfacial chemistry can be addressed through the perspective of solid-state NMR characterization techniques.

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Section: Interfaces In Nanoporous Materialsmentioning

confidence: 99%

Section: Interfaces In Nanoporous Materialsmentioning

confidence: 99%

Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid‐State NMR

et al. 2017

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“…For example, Zn (used in this work) has only one NMR-active isotope ( 67 Zn, I ¼ 5/2) with a relatively low γ and low natural abundance of 4.1% (resulting in a receptivity, relative to 1 H, of 1.18 Â 10 À4 ). Spectral acquisition is further hindered by the presence of a relatively large quadrupole moment (which, coupled with the low γ, produces significant quadrupolar broadening), often necessitating the use of high magnetic fields [19][20][21][22]. Even when resolution is increased through the use of techniques such as MAS, complex and overlapping spectral lineshapes are often still observed in NMR spectra of solids, particularly for disordered materials [23].…”

Section: Introductionmentioning

confidence: 99%

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

Sneddon

Kahr

Orsi

et al. 2017

Solid State Nuclear Magnetic Resonance

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Zeolitic imidazolate frameworks (ZIFs) are a subclass of metal-organic frameworks (MOFs) with extended threedimensional networks of transition metal nodes (bridged by rigid imidazolate linkers), with potential applications in gas storage and separation, sensing and controlled delivery of drug molecules. Here, we investigate the use of 13 C and 15 N solid-state NMR spectroscopy to characterise the local structure and disorder in a variety of singleand dual-linker ZIFs. In most cases, a combination of a basic knowledge of chemical shifts typically observed in solution-state NMR spectroscopy and the use of dipolar dephasing NMR experiments to reveal information about quaternary carbon species are combined to enable spectral assignment. Accurate measurement of the anisotropic components of the chemical shift provided additional information to characterise the local environment and the possibility of trying to understand the relationships between NMR parameters and both local and long-range structure. First-principles calculations on some of the simpler, ordered ZIFs were possible, and provided support for the spectral assignments, while comparison of these model systems to more disordered ZIFs aided interpretation of the more complex spectra obtained. It is shown that 13 C and 15 N NMR are sufficiently sensitive to detect small changes in the local environment, e.g., functionalisation of the linker, crystallographic inequivalence and changes to the framework topology, while the relative proportion of each linker present can be obtained by comparing relative intensities of resonances corresponding to chemically-similar species in cross polarisation experiments with short contact times. Therefore, multinuclear NMR spectroscopy, and in particular the measurement of both isotropic and anisotropic parameters, offers a useful tool for the structural study of ordered and, in particular, disordered ZIFs.

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“…Solid-state NMR (SSNMR) experiments have been shown to yield detailed shortrange structural information in a wide variety of materials, including MOFs. [14][15][16][17] Prior studies of MIL-53 (lt) using 1 H and 13 C SSNMR experiments, in conjunction with pXRD experiments, have provided valuable insights into the hydrogen-bonding network between guest H 2 O molecules and the framework. 18 Other nuclei, such as 2 H and 45 Sc, have also been used to probe the MIL-53 system.…”

Section: Introductionmentioning

confidence: 99%

Investigating adsorption of organic compounds in metal-organic framework MIL-53

Ibrahim

et al. 2015

Can. J. Chem.

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Metal-organic frameworks (MOFs) are versatile materials that incorporate metal centers along with organic linkers in highly ordered, intricate structures. MIL-53 is a MOF that exhibits a "breathing effect," where the pore size and MOF topology are profoundly influenced by the identity and binding mechanism of guest molecules. This phenomenon renders MIL-53 a promising candidate for sensing applications. In this report, the adsorption of various organic compounds within MIL-53 is investigated using a combination of complementary techniques. Thermal gravimetric analysis experiments confirm loading of the guest molecules and yield insight into adsorption interactions and strengths. Significant guest-induced changes in the crystal structure of MIL-53 are revealed by powder X-ray diffraction experiments; specific unique phases of MIL-53 are related to the identity of the guest molecule and its binding mechanism to the framework. 27 Al and 13 C solid-state NMR experiments probe the interaction between guest molecules and MIL-53. The relationship between the nature of the guest, the structure of MIL-53, and 27 Al NMR parameters is explored. 27 Al NMR parameters are sensitive to the host-guest binding mechanism (i.e., hydrogenbonding or -stacking interactions) and yield valuable information regarding the influence of the adsorbates on the local aluminum environment. This combination of physical characterization techniques is a useful probe of guest adsorption and the breathing effect within MIL-53 and should prove useful for investigation of related MOFs. Résumé: Les réseaux métallo-organiques (MOF, acronyme anglais pour Metal-Organic Frameworks) sont des matériaux polyvalents où des centres métalliques sont incorporés dans un réseau organique formant des structures complexes et hautement ordonnées. Le MIL-53 est un réseau métallo-organique présentant un « effet de respiration », dont la taille des pores et la topologie du réseau métallo-organique dépendent fortement de l'identité et du mécanisme de liaison des molécules invitées. Ce phénomène fait du MIL-53 un candidat prometteur pour des applications dans le domaine des capteurs. Dans les présents travaux, nous avons étudié l'adsorption de divers composés organiques au MIL-53 à l'aide d'un ensemble de techniques complémentaires. Des analyses thermogravimétriques confirment la charge de molécules invitées et fournissent un aperçu des interactions et des forces d'adsorption. Des expériences de diffraction des rayons X sur poudre ont permis de révéler des modifications importantes de la structure cristalline du MIL-53 induites par l'invité; des phases uniques propres au MIL-53 sont liées à l'identité de l'invité et à son mécanisme de liaison au réseau. Des expériences de RMN 27 Al et 13 C à l'état solide ont permis d'explorer les interactions entre les molécules invitées et le MIL-53. Nous avons étudié la relation entre la nature de l'invité, la structure du MIL-53 et les paramètres RMN 27 Al. Ces derniers sont sensibles au mécanisme de liaison hôte-invité (c.-à -d. les l...

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Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR

Cited by 59 publications

References 93 publications

Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid‐State NMR

Understanding Surface and Interfacial Chemistry in Functional Nanomaterials via Solid‐State NMR

Investigation of zeolitic imidazolate frameworks using 13 C and 15 N solid-state NMR spectroscopy

Investigating adsorption of organic compounds in metal-organic framework MIL-53

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