17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Ohlin, C. André; Casey, William H.

doi:10.1016/bs.arnmr.2018.01.001

Cited by 8 publications

(10 citation statements)

References 176 publications

(290 reference statements)

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“…Therefore, the characterization of oxygen local electronic and geometric environments is very important. 17 O solid-state NMR (SSNMR) spectroscopy has become an ideal site-specific characterization tool for probing oxygen local environments, as 17 O is sensitive to the chemical shift and quadrupolar interactions, − has a large diagnostic chemical shift range, − and is influenced by coupling to neighboring NMR-active nuclei (e.g., 1 H, 13 C, and 15 N). − There has been tremendous progress made in NMR methodology and technology in recent years, yet the potential of 17 O SSNMR for uncovering detailed structural and bonding information in oxygen-containing compounds has been limited by the inherently low sensitivity and resolution resulting from the very low natural abundance (0.038%), relatively low gyromagnetic ratio (γ = −5.774 MHz T –1 ), and quadrupolar nature (spin I = 5/2) of 17 O …”

Section: Introductionmentioning

confidence: 99%

Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

Martins

Wang

et al. 2020

J. Am. Chem. Soc.

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The spectroscopic study of oxygen, a vital element in materials, physical, and life sciences, is of tremendous fundamental and practical importance. 17 O solid-state NMR (SSNMR) spectroscopy has evolved into an ideal site-specific characterization tool, furnishing valuable information on the local geometric and bonding environments about chemically distinct and, in some favorable cases, crystallographically inequivalent oxygen sites. However, 17 O is a challenging nucleus to study via SSNMR, as it suffers from low sensitivity and resolution, owing to the quadrupolar interaction and low 17 O natural abundance. Herein, we report a significant advance in 17 O SSNMR spectroscopy. 17 O isotopic enrichment and the use of an ultrahigh 35.2 T magnetic field have unlocked the identification of many inequivalent carboxylate oxygen sites in the as-made and activated phases of the metal−organic framework (MOF) α-Mg 3 (HCOO) 6 . The subtle 17 O spectral differences between the as-made and activated phases yield detailed information about host−guest interactions, including insight into nonconventional O•••H−C hydrogen bonding. Such weak interactions often play key roles in the applications of MOFs, such as gas adsorption and biomedicine, and are usually difficult to study via other characterization routes. The power of performing 17 O SSNMR experiments at an ultrahigh magnetic field of 35.2 T for MOF characterization is further demonstrated by examining activation of the MIL-53(Al) MOF. The sensitivity and resolution enhanced at 35.2 T allows partially and fully activated MIL-53(Al) to be unambiguously distinguished and also permits several oxygen environments in the partially activated phase to be tentatively identified. This demonstration of the very high resolution of 17 O SSNMR recorded at the highest magnetic field accessible to chemists to date illustrates how a broad variety of scientists can now study oxygen-containing materials and obtain previously inaccessible fine structural information.

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Section: Introductionmentioning

confidence: 99%

Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

Martins

Wang

et al. 2020

J. Am. Chem. Soc.

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“…This allows studying the rates of oxygen-isotope exchange between solvent and POM molecules sites and has been proven useful for understanding of POMs equilibria. 36,37 31 P NMR. The large number and wide variety of heteropoly compounds with phosphorus as a heteroatom led to a significant development of 31 P NMR, which shows a high sensitivity of its chemical shift based on POMs composition.…”

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confidence: 99%

Polyoxometalates in solution: speciation under spotlight

2020

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“…17 O solid-state NMR has been extensively employed in recent years, specifically because of its wide chemical shift range and the high sensitivity of its quadrupolar coupling constant to the local symmetry. − Here we use 17 O NMR to obtain a deeper understanding of the structure of the anionic sublattice. The 17 O NMR spectrum for the isotope labeled yttrium-oxyhydride thin film (Figure a) shows the central transition (CT, expanded in Figure b) and the spinning sideband manifold of the satellite transitions due to the quadrupolar interaction.…”

Section: Resultsmentioning

confidence: 99%

Exploring Multi-Anion Chemistry in Yttrium Oxyhydrides: Solid-State NMR Studies and DFT Calculations

Banerjee¹,

Chaykina

Stigter

et al. 2023

J. Phys. Chem. C

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Rare earth oxyhydrides REO x H (3−2x) , with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O 2− :H − ) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use 1 H, 2 H, 17 O, and 89 Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YO x H (3−2x) with both anionordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional 17 O− 1 H and 89 Y− 1 H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YO x H (3−2x) ) is determined by comparing static 1 H NMR line widths with calculated 1 H− 1 H dipolar couplings of yttrium oxyhydride models. The 1D 17 O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH − ) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H + + H − → H 2 ). 1 H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H 2 in the lattice.

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17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Cited by 8 publications

References 176 publications

Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

Polyoxometalates in solution: speciation under spotlight

Exploring Multi-Anion Chemistry in Yttrium Oxyhydrides: Solid-State NMR Studies and DFT Calculations

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17 O NMR as a Tool in Discrete Metal Oxide Cluster Chemistry

Cited by 8 publications

References 176 publications

Higher Magnetic Fields, Finer MOF Structural Information: 17O Solid-State NMR at 35.2 T

Higher Magnetic Fields, Finer MOF Structural Information: 17O Solid-State NMR at 35.2 T

Polyoxometalates in solution: speciation under spotlight

Exploring Multi-Anion Chemistry in Yttrium Oxyhydrides: Solid-State NMR Studies and DFT Calculations

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Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T

Higher Magnetic Fields, Finer MOF Structural Information: ¹⁷O Solid-State NMR at 35.2 T