Influence of F content on the composition of Al-rich synthetic phlogopite: Part II. Probing the structural arrangement of aluminum in tetrahedral and octahedral layers by27Al MQMAS and1H/19F-27Al HETCOR and REDOR experiments

Fechtelkord, Michael; Behrens, Harald; Holtz, François; Bretherton, Jeremy L.; Fyfe, C. A.; Groat, Lee A.; Raudsepp, Mati

doi:10.2138/am-2003-0713

Cited by 28 publications

(54 citation statements)

References 22 publications

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“…Rotor-synchronised acquisition in the first dimension was used, yielding a spectral width of 30 kHz. Typically, 64 t 1 FIDs (free induction decays) were acquired using a 7.5 ms radio-frequency (rf) pulse length for 908 pulses (rf field strength = 33 kHz), and a recycle delay of 3 s. Al two-dimensional HETCOR experiments used to establish the spatial connectivity between framework aluminium sites and protons [32][33][34][35] were based on a standard 1 H- 27 Al cross-polarisation experiment in which an incremented period was inserted between t 1 (the 1 H 908 pulse) and the contact time. Because the heteronuclear dipolar couplings depended strongly on 1/r 3 where in this case r = Al-H internuclear distance, only the correlation between neighbouring atoms was observed.…”

Section: Methodsmentioning

confidence: 99%

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

Haouas

Volkringer

Loiseau

et al. 2009

Chemistry A European J

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A changeable character: Differences in the dynamics of occluded moieties within the large pores (see graphic) of aluminium 1,3,5-benzene tricarboxylate framework solid MIL-110 are a function of the synthesis pH. Host-guest proton-transfer processes lead to a reversible change in the character of the framework from cationic to neutral, depending on the nature of the extra-framework moieties.The aluminium 1,3,5-benzene tricarboxylate framework solid MIL-110, which crystallises either at pH approximately 0 or at pH approximately 4, has been investigated by solid-state NMR spectroscopy. At pH approximately 0 the solid (MIL-110{pH0}) is the unique stable thermodynamic product, whereas at pH approximately 4 MIL-110{pH4} is observed as a kinetic product in competition with the MIL-96 phase. Diffraction studies and (27)Al NMR spectroscopy prove that the framework is identical in both cases. The nature and dynamics of occluded moieties within the large pores look quite different for the two compounds. MIL-110{pH4} and MIL-110{pH0} both show the presence of occluded 1,3,5-benzene tricarboxylate (btc), with additional nitrates and water molecules. However, the proportions of btc, nitrates and water are functions of the pH, leading to an identical framework and a quite different extra-framework. With the extra-framework moieties, the framework undergoes a proton transfer which is a function of the synthesis pH. Washing the MIL-110{pH0} phase with water produces a different extra-framework structure, richer in water and poorer in btc and nitrates. The hydroxyl groups of the inorganic aluminium cluster of the framework are involved in a proton transfer, which leads for all cases to a cationic framework and an anionic extra-framework. (1)H-(1)H DQ 2D NMR spectra (DQ=double quantum) give evidence for the interaction of extra-framework btc with the terminal water carried by Al(2,3) and shows their proximity to the closest hydroxyl groups. A structure for the non-diffracting extra-framework is proposed as the most plausible topology. It provides an efficient picture for the creation of many substituted MIL-110 compounds that would have a large number of applications.

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Section: Methodsmentioning

confidence: 99%

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

Haouas

Volkringer

Loiseau

et al. 2009

Chemistry A European J

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“…The use of 27 Al NMR can provide important structural information relating to the local order around aluminium atoms in crystalline and disordered compounds. Numerous 27 Al NMR studies have been performed on a wide range of chemical systems.…”

Section: Introductionmentioning

confidence: 99%

“…Numerous 27 Al NMR studies have been performed on a wide range of chemical systems. Oxide minerals have been particularly well studied.…”

Section: Introductionmentioning

confidence: 99%

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The Relationship Between ²⁷Al Quadrupolar Parameters and AlF₆^3– Octahedron Connectivity in Crystalline and Glassy Fluoroaluminates

et al. 2007

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Abstract27Al SATRAS and MQ‐MAS spectra were recorded for eight crystalline compounds, from the CaF2–AlF3 and BaF2–AlF3 binary and BaF2–CaF2–AlF3 ternary systems, and four glass compositions with different CaF2/BaF2/AlF3 contents. For the crystalline phases, the reconstruction of the spectra leads to the precise determination of the NMR parameters. For the glassy phases, the 27Al SATRAS spectra have been reconstructed using quadrupolar parameter distributions. The main finding of this study is the dependence of the quadrupolar frequency on the type of AlF63– octahedron connectivity. For crystalline phases the experimental νQ values range between 75 kHz and 510 kHz for structures built up from isolated octahedra, and are between 560 kHz and 1250 kHz for structures built up from isolated chains of cis‐connected octahedra, and are between 1530 kHz and 1580 kHz for structures built up from isolated chains of trans‐connected octahedra. In the glassy phases the maximum of the quadrupolar frequency distribution shifts toward larger values and its width increases with increasing AlF3 content, and subsequently with the number of connected octahedra. The range of the νQ values seems to indicate that when the octahedra are connected, cis connections occur most frequently. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…The fit converged on a global solution for the chemical shift tensors (listed in Table 2, Table 3 and Table 4) and the initial orientation of the c-axis in the LAB frame at θ = (62.58 Ϯ 0.09)°, φ = (328.8 Ϯ 0.1)°. For the 207 Pb tensor eigenvalues, the corre- (7) 0.0815 (8) sponding numbers of vanadinite have also been included into Table 3 and Table 4. The anisotropy of the chemical shift tensors, measured by Δδ, is smaller for pyromorphite, but still relatively large, reflecting the presence of an electron lone pair at the 207 Pb.…”

Section: Tensor Eigenvalues From Nmr Spectroscopymentioning

confidence: 99%

Determination of the ³¹P and ²⁰⁷Pb Chemical Shift Tensors in Pyromorphite, Pb₅(PO₄)₃Cl, by Single‐Crystal NMR Measurements and DFT Calculations

Zeman

Moudrakovski

Hoch

et al. 2017

Zeitschrift anorg allge chemie

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Abstract. The chemical shift (CS) tensors for 31 P and 207 Pb in the natural mineral pyromorphite, Pb 5 (PO 4 ) 3 Cl, were determined from orientation-dependent NMR spectra of a single crystal, and MAS-NMR spectroscopic experiments. For the two crystallographically independent lead atoms in the hexagonal crystal lattice with space group P6 3 /m, the NMR parameters derived from the tensor eigenvalues are δ iso = -2172 ppm, η cs = 0.08 for the 207 Pb at Wyckoff position 6h, and δ iso = -2810 ppm, η cs = 0.49 for position 4f. For the 31 P, which are also located at positions 6h, δ iso = -1.74 ppm and η cs = 0.21 was found. A multi-parameter fit was utilized to extract the tensors from spectra

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Influence of F content on the composition of Al-rich synthetic phlogopite: Part II. Probing the structural arrangement of aluminum in tetrahedral and octahedral layers by²⁷Al MQMAS and¹H/¹⁹F-²⁷Al HETCOR and REDOR experiments

Cited by 28 publications

References 22 publications

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Relationship Between ²⁷Al Quadrupolar Parameters and AlF₆^3– Octahedron Connectivity in Crystalline and Glassy Fluoroaluminates

Determination of the ³¹P and ²⁰⁷Pb Chemical Shift Tensors in Pyromorphite, Pb₅(PO₄)₃Cl, by Single‐Crystal NMR Measurements and DFT Calculations

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Influence of F content on the composition of Al-rich synthetic phlogopite: Part II. Probing the structural arrangement of aluminum in tetrahedral and octahedral layers by27Al MQMAS and1H/19F-27Al HETCOR and REDOR experiments

Cited by 28 publications

References 22 publications

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Extra‐Framework Sub‐Lattice of the Metal–Organic Framework MIL‐110: A Solid‐State NMR Investigation

The Relationship Between 27Al Quadrupolar Parameters and AlF63– Octahedron Connectivity in Crystalline and Glassy Fluoroaluminates

Determination of the 31P and 207Pb Chemical Shift Tensors in Pyromorphite, Pb5(PO4)3Cl, by Single‐Crystal NMR Measurements and DFT Calculations

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Influence of F content on the composition of Al-rich synthetic phlogopite: Part II. Probing the structural arrangement of aluminum in tetrahedral and octahedral layers by²⁷Al MQMAS and¹H/¹⁹F-²⁷Al HETCOR and REDOR experiments

The Relationship Between ²⁷Al Quadrupolar Parameters and AlF₆^3– Octahedron Connectivity in Crystalline and Glassy Fluoroaluminates

Determination of the ³¹P and ²⁰⁷Pb Chemical Shift Tensors in Pyromorphite, Pb₅(PO₄)₃Cl, by Single‐Crystal NMR Measurements and DFT Calculations