Cost-effective<sup>17</sup>O enrichment and NMR spectroscopy of mixed-metal terephthalate metal–organic frameworks

Bignami, Giulia P. M.; Davis, Zachary; Dawson, Daniel M.; Morris, Samuel A.; Russell, Samantha; McKay, David; Parke, Richard E.; Iuga, Dinu; Morris, Russell E.; Ashbrook, Sharon E.

doi:10.1039/c7sc04649a

Cited by 55 publications

(185 citation statements)

References 63 publications

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“…In contrast, the V IV =O EPR spectra for the np-h and as states reveal that at least two distinct dopant sites exist, as indicated by arrows in Figure 1. Similar conclusions on inequivalence of the metal sites in these two states were obtained from magic angle spinning nuclear magnetic resonance studies [15,16]. Finally, exposure of the MOF to O2 (paramagnetic), either pure or in air, led to a marked EPR linewidth increase for frameworks in the lp state, but had virtually no effect for the three other states.…”

Section: Introductionsupporting

confidence: 73%

EPR characterization of vanadium dopant sites in DUT-5(Al)

et al. 2019

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The structural environment of the V IV ions doped in the metal-organic framework (MOF) DUT-5(Al) ((Al III OH)BPDC) was studied with electron paramagnetic resonance (EPR). At low V concentrations, two different vanadyl components are observed in the EPR spectrum: a broad-line component, best visible at ambient air conditions, and a narrow-line component, becoming more prominent at lower pressures. Recording the EPR spectra at both X-and Qband, spin-Hamiltonian parameters were derived for both components. Similarities between the spectrum of the narrow-line component and the spectrum of V IV centers in the large pore state of a related MOF, MIL-53(Al) ((Al III OH)BDC), are discussed, including their sensitivity to oxygen. The broad-line component cannot conclusively be identified by comparison with V IV centers in MIL-53(Al). Increasing the concentration of V IV in the DUT-5(Al) framework, a third vanadyl component appears in the spectrum, together with a broad feature related to the spectrum of COMOC-2(V) ((V IV =O)BPDC). Surprisingly, this third component appears to be linked with a narrow pore state of the mixed-metal MOF.

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Section: Introductionsupporting

confidence: 73%

EPR characterization of vanadium dopant sites in DUT-5(Al)

et al. 2019

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“…17 O required in a synthesis or reaction, such as dry gel conversion methods, ionothermal reactions, or the use of very low reaction volumes, have been employed to reduce the cost of producing enriched material. [78][79][80][81] In addition to the improvement in sensitivity, enrichment has further advantages, including the possibility to utilize other interactions (such as the 2 H quadrupolar interaction to study dynamics, as discussed above) or the use of selective enrichment to aid spectral assignment 82,83 or simplify complex spectra of biomolecules. 83 It is also possible to improve the efficiency of many NMR experiments by careful choice/optimisation of the RF pulse sequence used.…”

Section: Sensitivity Enhancementmentioning

confidence: 99%

Perspective: Current advances in solid-state NMR spectroscopy

Ashbrook

Hodgkinson

2018

The Journal of Chemical Physics

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In contrast to the rapid and revolutionary impact of solution-state Nuclear Magnetic Resonance (NMR) on modern chemistry, the field of solid-state NMR has matured more slowly. This reflects the major technical challenges of much reduced spectral resolution and sensitivity in solid-state as compared to solution-state spectra, as well as the relative complexity of the solid state. In this perspective, we outline the technique developments that have pushed resolution to intrinsic limits and the approaches, including ongoing major developments in the field of Dynamic Nuclear Polarisation, that have enhanced spectral sensitivity. The information on local structure and dynamics that can be obtained using these gains in sensitivity and resolution is illustrated with a diverse range of examples from large biomolecules to energy materials and pharmaceuticals and from both ordered and highly disordered materials. We discuss how parallel developments in quantum chemical calculation, particularly density functional theory, have enabled experimental data to be translated directly into information on local structure and dynamics, giving rise to the developing field of "NMR crystallography."

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“…[70a] By using 17 OM AS-NMR spectroscopy,B ignami et al were able to determine the distribution of Al and Ga in mixed-metal MIL-53 materials. [90] They analyzedt he signals originating from the metal bridging hydroxyl groups and found that only as mall proportion of the hydroxyl groups bridged an Al/Ga pair,w hile most of the hydroxyl groups bridged Al/Al or Ga/Ga pairs.…”

Section: Characterization Of Mixed-metal Mofsmentioning

confidence: 99%

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Bitzer

Kleist

2019

Chemistry A European J

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In recent years, the synthesis of mixed‐metal and mixed‐linker metal–organic frameworks with multiple metals and/or linker molecules combined in one framework has become a growing field of interest. These mixed‐component or multivariate metal–organic framework materials provide the possibility to introduce multiple functionalities inside one framework. The interaction of guest molecules with different functionalities in the same material is a promising approach in the fields of gas storage, separation, catalysis and drug delivery. Furthermore, the combination of different components may lead to synergistic effects that cannot be achieved otherwise. These mixed‐component approaches open up new pathways to an even larger range of possible customizations in the field of metal–organic frameworks.

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Cost-effective¹⁷O enrichment and NMR spectroscopy of mixed-metal terephthalate metal–organic frameworks

Abstract: Cost-effective 17O enrichment of metal–organic frameworks enables the composition and disorder in mixed-metal materials to be determined using NMR spectroscopy.

Cited by 55 publications

References 63 publications

EPR characterization of vanadium dopant sites in DUT-5(Al)

EPR characterization of vanadium dopant sites in DUT-5(Al)

Perspective: Current advances in solid-state NMR spectroscopy

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

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Cost-effective17O enrichment and NMR spectroscopy of mixed-metal terephthalate metal–organic frameworks

Abstract: Cost-effective 17O enrichment of metal–organic frameworks enables the composition and disorder in mixed-metal materials to be determined using NMR spectroscopy.

Cited by 55 publications

References 63 publications

EPR characterization of vanadium dopant sites in DUT-5(Al)

EPR characterization of vanadium dopant sites in DUT-5(Al)

Perspective: Current advances in solid-state NMR spectroscopy

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

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Product

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Cost-effective¹⁷O enrichment and NMR spectroscopy of mixed-metal terephthalate metal–organic frameworks