Recent Advances in Solid-State 67Zn NMR Studies

Huang, Yining; Sutrisno, Andre

doi:10.1016/b978-0-12-800185-1.00001-2

Cited by 17 publications

(29 citation statements)

References 102 publications

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“…The 67 Zn CT powder pattern is dominated by the CS interaction, with Ω ( 67 Zn)=8.8 ppm, κ ( 67 Zn)=−1.0, and δ iso ( 67 Zn)=−17.9 ppm. The δ iso ( 67 Zn) value resides in the normal range for six‐coordinate zinc oxoanion compounds 20b. 33 To the best of our knowledge, this is the smallest 67 Zn CS anisotropy (CSA, measured by Ω ) that has been accurately determined and reported 20b…”

Section: Resultsmentioning

confidence: 94%

“…67 Zn SSNMR spectroscopy has been used to investigate and characterize a wide variety of materials, ranging from bioinorganic compounds to nanoparticles,20b and has shown to be a sensitive probe of the local Zn environment in several MOFs 20c. 22c, 32 67 Zn SSNMR spectra are challenging to acquire, since 67 Zn is a quadrupolar nucleus ( I =5/2) with a relatively low gyromagnetic ratio of γ ( 67 Zn)=1.677×10 7 rad T −1 s −1 , a very low natural abundance of 4.1 %,30 and a moderate Q ( 67 Zn) of 150 mbarn 29.…”

Section: Resultsmentioning

confidence: 99%

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Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Lucier

Sinelnikov

et al. 2015

Chemistry A European J

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The paraelectric-ferroelectric phase transition in two isostructural metal-organic frameworks (MOFs) [NH4 ][M(HCOO)3 ] (M=Mg, Zn) was investigated by in situ variable-temperature (25) Mg, (67) Zn, (14) N, and (13) C solid-state NMR (SSNMR) spectroscopy. With decreasing temperature, a disorder-order transition of NH4 (+) cations causes a change in dielectric properties. It is thought that [NH4 ][Mg(HCOO)3 ] exhibits a higher transition temperature than [NH4 ][Zn(HCOO)3 ] due to stronger hydrogen-bonding interactions between NH4 (+) ions and framework oxygen atoms. (25) Mg and (67) Zn NMR parameters are very sensitive to temperature-induced changes in structure, dynamics, and dielectric behavior; stark spectral differences across the paraelectric-ferroelectric phase transition are intimately related to subtle changes in the local environment of the metal center. Although (25) Mg and (67) Zn are challenging nuclei for SSNMR experiments, the highly spherically symmetric metal-atom environments in [NH4 ][M(HCOO)3 ] give rise to relatively narrow spectra that can be acquired in 30-60 min at a low magnetic field of 9.4 T. Complementary (14) N and (13) C SSNMR experiments were performed to probe the role of NH4 (+) -framework hydrogen bonding in the paraelectric-ferroelectric phase transition. This multinuclear SSNMR approach yields new physical insights into the [NH4 ][M(HCOO)3 ] system and shows great potential for molecular-level studies on electric phenomena in a wide variety of MOFs.

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Lucier

Sinelnikov

et al. 2015

Chemistry A European J

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“…The Zn atoms occupy the same sites as the Cd atoms in both I 4̅ and I 4̅2 m structures if the disorder of only these atoms is assumed to take place. Although 67 Zn NMR spectra ( I = 5/2; 4.1% natural abundance, Q = 15.0 fm 2 , Ξ = 6.3%) are quite challenging to measure, ,− they were obtained for Cu 2 ZnSnS 4 and Cu 2 Zn 0.8 Cd 0.2 SnS 4 (Figure c). For Cu 2 ZnSnS 4 , a single resonance is observed at 358 ppm with no second-order contribution and a small EFG ( C Q < 1 MHz), consistent with a unique Zn site at [2 d (0, 1/2, 3/4; 1/2, 0, 1/4)].…”

Section: Results and Discussionmentioning

confidence: 99%

Mere Anarchy is Loosed: Structural Disorder in Cu₂Zn_1–xCd_xSnS₄

et al. 2021

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Substitution of Cd into the photovoltaic material Cu2ZnSnS4 has been previously shown to improve power conversion efficiencies, and although various models for the structural disorder have been proposed, full characterization of Cu2Zn1–x Cd x SnS4 has been hampered by a lack of understanding about the local structure around individual atoms. Through a combination of powder X-ray diffraction and solid-state NMR spectroscopy (119Sn, 113Cd, 63Cu, and 67Zn), the detailed structures of the entire series Cu2Zn1–x Cd x SnS4 (x = 0–1), prepared as bulk samples by reaction of the elements at 800 °C, have been examined. The ordered kesterite structure in space group I4̅ of the end-member Cu2ZnSnS4 (x = 0) was retained up to Cu2Zn0.7Cd0.3SnS4 (x = 0.3) and the stannite structure in space group I4̅2m from Cu2Zn0.6Cd0.4SnS4 (x = 0.4) to the end-member Cu2CdSnS4 (x = 1). Although the structural transition at x = 0.4 was confirmed, 113Cd NMR spectroscopy reveals the coexistence of phases with I4̅ and I4̅2m structures in the intermediate region (x = 0.3–0.4), evidence for which was previously unattainable from XRD data alone. The 119Sn NMR spectra indicated the presence of Sn sites surrounded within distinct local chemical environments imparted by the distribution of Zn and Cd atoms disordered within the second coordination sphere, which could be resolved by their isotropic chemical shifts and quantified by their peak areas. Ultrahigh-field (21.1 T) 63Cu NMR spectroscopy revealed the two sets of Cu sites in the I4̅ structure expected for the lightly Cd-substituted members (up to Cu2Zn0.8Cd0.2SnS4) and one set of Cu sites in the I4̅2m structure for the more heavily substituted members. The balance of evidence from the comparison of experimental and DFT-computed 63Cu and 67Zn NMR spectra suggests that Cu/Zn disorder does not occur. Instead, Cd substitution in Cu2Zn1–x Cd x SnS4 proceeds exclusively through disorder of Zn and Cd atoms, at least in the bulk samples examined.

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“…32, 34 67 Zn NMR spectroscopy has been used to characterize the coordination geometry around Zn +2 ions in pure compounds. 49,[85][86][87][88][89] In particular, the natural-abundance 67 Zn NMR spectra of ZnO at 11.7 and 14.1 T have been reported. 86,87 The line shape of the central-transition is determined by second-order quadrupole effects, and for ZnO C Q = 2.4 MHz, η Q = 0, and δ iso = 240 ppm relative to a 0.1 M ZnCl 2 aqueous solution.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Multi-technique structural analysis of zinc carboxylates (soaps)

et al. 2023

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Recent Advances in Solid-State 67Zn NMR Studies

Cited by 17 publications

References 102 publications

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Mere Anarchy is Loosed: Structural Disorder in Cu₂Zn_1–xCd_xSnS₄

Multi-technique structural analysis of zinc carboxylates (soaps)

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Recent Advances in Solid-State 67Zn NMR Studies

Cited by 17 publications

References 102 publications

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH4][M(HCOO)3] by Solid‐State NMR Spectroscopy

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH4][M(HCOO)3] by Solid‐State NMR Spectroscopy

Mere Anarchy is Loosed: Structural Disorder in Cu2Zn1–xCdxSnS4

Multi-technique structural analysis of zinc carboxylates (soaps)

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Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Monitoring and Understanding the Paraelectric–Ferroelectric Phase Transition in the Metal–Organic Framework [NH₄][M(HCOO)₃] by Solid‐State NMR Spectroscopy

Mere Anarchy is Loosed: Structural Disorder in Cu₂Zn_1–xCd_xSnS₄