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Special Issue "Solid-State NMR Spectroscopy in Materials Chemistry"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (15 December 2019).

Special Issue Editor

Prof. Mattias Edén
Website
Guest Editor
Department of Materials and Environmental Chemistry, Stockholm University, SE 10691 Stockholm, Sweden
Interests: solid state NMR; disordered materials; oxide-based glasses; glass structure; bioactive glasses; biomineralization; molecular dynamics simulations; spin dynamics simulations; rf-pulse sequence design in magic-angle spinning NMR

Special Issue Information

Dear Colleagues,

The element-specific and non-invasive nature of solid-state nuclear magnetic resonance (NMR) spectroscopy, coupled with its ability to readily probe structures across a subnanometer scale, have rendered it a ubiquitous method for studying structure and dynamics in vast groups of structurally ordered, as well as disordered materials. Solid-state NMR spectroscopy is continuously developing concerning enhancements of signal sensitivity and resolution. Notably, dynamic nuclear polarization (DNP) NMR has opened up new avenues for probing species at very low concentrations, whereas “NMR crystallography” combines solid-state NMR experiments with density functional theory calculations for solving structures.

For this Special Issue, we invite new scientific reports as well as reviews on “Solid-State NMR Spectroscopy in Materials Chemistry”, taken in its broadest scope/meaning—encompassing investigations on the structure, order, and dynamics of materials by solid-state NMR, as well as developments of new such techniques. We also welcome submissions on the application of solid-state NMR for monitoring chemical processes, ranging from sol–gel preparations to solid-state chemistry, as well as to material-related problems in fields such as catalysis, biomineralization, and green chemistry.

Prof. Mattias Edén
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Structure, order, dynamics
  • DFT calculations of NMR parameters
  • NMR crystallography
  • Ceramics, glasses, minerals
  • Porous materials, nanomaterials
  • Biomaterials, polymers, soft matter
  • Composites, organic/inorganic hybrid materials
  • Surfaces, interfaces, catalysis
  • Structure–composition–property relationships
  • New solid-state NMR techniques
  • Dynamic nuclear polarization

Published Papers (9 papers)

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Editorial

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Open AccessEditorial
Editorial for the Special Issue on Solid-State NMR Spectroscopy in Materials Chemistry
Molecules 2020, 25(12), 2720; https://doi.org/10.3390/molecules25122720 - 12 Jun 2020
Abstract
Nuclear Magnetic Resonance (NMR) has, over the past few decades, emerged as the most powerful spectroscopic technique for studying molecular structure across a sub-nanometer scale, as well as for probing molecular dynamics over widely spanning timescales (ns to s) [...] Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)

Research

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Open AccessArticle
Computational and Experimental 1H-NMR Study of Hydrated Mg-Based Minerals
Molecules 2020, 25(4), 933; https://doi.org/10.3390/molecules25040933 - 19 Feb 2020
Cited by 2
Abstract
Magnesium oxide (MgO) can convert to different magnesium-containing compounds depending on exposure and environmental conditions. Many MgO-based phases contain hydrated species allowing 1H-nuclear magnetic resonance (NMR) spectroscopy to be used in the characterization and quantification of proton-containing phases; however, surprisingly limited examples [...] Read more.
Magnesium oxide (MgO) can convert to different magnesium-containing compounds depending on exposure and environmental conditions. Many MgO-based phases contain hydrated species allowing 1H-nuclear magnetic resonance (NMR) spectroscopy to be used in the characterization and quantification of proton-containing phases; however, surprisingly limited examples have been reported. Here, 1H-magic angle spinning (MAS) NMR spectra of select Mg-based minerals are presented and assigned. These experimental results are combined with computational NMR density functional theory (DFT) periodic calculations to calibrate the predicted chemical shielding results. This correlation is then used to predict the NMR shielding for a series of different MgO hydroxide, magnesium chloride hydrate, magnesium perchlorate, and magnesium cement compounds to aid in the future assignment of 1H-NMR spectra for complex Mg phases. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessArticle
Local Electronic Structure in AlN Studied by Single-Crystal 27Al and 14N NMR and DFT Calculations
Molecules 2020, 25(3), 469; https://doi.org/10.3390/molecules25030469 - 22 Jan 2020
Cited by 2
Abstract
Both the chemical shift and quadrupole coupling tensors for 14 N and 27 Al in the wurtzite structure of aluminum nitride have been determined to high precision by single-crystal NMR spectroscopy. A homoepitaxially grown AlN single crystal with known morphology was used, which [...] Read more.
Both the chemical shift and quadrupole coupling tensors for 14 N and 27 Al in the wurtzite structure of aluminum nitride have been determined to high precision by single-crystal NMR spectroscopy. A homoepitaxially grown AlN single crystal with known morphology was used, which allowed for optical alignment of the crystal on the goniometer axis. From the analysis of the rotation patterns of 14 N ( I = 1 ) and 27 Al ( I = 5 / 2 ), the quadrupolar coupling constants were determined to χ ( 14 N ) = ( 8.19 ± 0.02 ) kHz, and χ ( 27 Al ) = ( 1.914 ± 0.001 ) MHz. The chemical shift parameters obtained from the data fit were δ i s o = ( 292.6 ± 0.6 ) ppm and δ Δ = ( 1.9 ± 1.1 ) ppm for 14 N, and (after correcting for the second-order quadrupolar shift) δ i s o = ( 113.6 ± 0.3 ) ppm and δ Δ = ( 12.7 ± 0.6 ) ppm for 27 Al. DFT calculations of the NMR parameters for non-optimized crystal geometries of AlN generally did not match the experimental values, whereas optimized geometries came close for 27 Al with χ ¯ calc = ( 1.791 ± 0.003 ) MHz, but not for 14 N with χ ¯ calc = ( 19.5 ± 3.3 ) kHz. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessFeature PaperArticle
Improved Magnetization Transfers among Quadrupolar Nuclei in Two-Dimensional Homonuclear Correlation NMR Experiments Applied to Inorganic Network Structures
Molecules 2020, 25(2), 337; https://doi.org/10.3390/molecules25020337 - 14 Jan 2020
Cited by 2
Abstract
We demonstrate that supercycles of previously introduced two-fold symmetry dipolar recoupling schemes may be utilized successfully in homonuclear correlation nuclear magnetic resonance (NMR) spectroscopy for probing proximities among half-integer spin quadrupolar nuclei in network materials undergoing magic-angle-spinning (MAS). These (SR2 2 [...] Read more.
We demonstrate that supercycles of previously introduced two-fold symmetry dipolar recoupling schemes may be utilized successfully in homonuclear correlation nuclear magnetic resonance (NMR) spectroscopy for probing proximities among half-integer spin quadrupolar nuclei in network materials undergoing magic-angle-spinning (MAS). These (SR2 2 1 ) M , (SR2 4 1 ) M , and (SR2 8 1 )M recoupling sequences with M = 3 and M = 4 offer comparably efficient magnetization transfers in single-quantum–single-quantum (1Q–1Q) correlation NMR experiments under moderately fast MAS conditions, as demonstrated at 14.1 T and 24 kHz MAS in the contexts of 11 B NMR on a Na 2 O–CaO–B 2 O 3 –SiO 2 glass and 27 Al NMR on the open framework aluminophosphate AlPO-CJ19 [(NH 4 ) 2 Al 4 (PO 4 ) 4 HPO 4 · H 2 O]. Numerically simulated magnetization transfers in spin–3/2 pairs revealed a progressively enhanced tolerance to resonance offsets and rf-amplitude errors of the recoupling pulses along the series (SR2 2 1 ) M < (SR2 4 1 ) M < (SR2 8 1 )M for increasing differences in chemical shifts between the two nuclei. Nonetheless, for scenarios of a relatively minor chemical-shift dispersions ( 3 kHz), the (SR2 2 1 )M supercycles perform best both experimentally and in simulations. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessArticle
Characterization of Phosphorus Species in Human Dentin by Solid-State NMR
Molecules 2020, 25(1), 196; https://doi.org/10.3390/molecules25010196 - 03 Jan 2020
Cited by 1
Abstract
The rat has been considered as an appropriate animal model for the study of the mineralization process in humans. In this work, we found that the phosphorus species in human dentin characterized by solid-state NMR spectroscopy consist mainly of orthophosphate and hydrogen phosphate. [...] Read more.
The rat has been considered as an appropriate animal model for the study of the mineralization process in humans. In this work, we found that the phosphorus species in human dentin characterized by solid-state NMR spectroscopy consist mainly of orthophosphate and hydrogen phosphate. Some orthophosphates are found in a disordered phase, where the phosphate ions are hydrogen-bonded to structural water, some present a stoichiometric apatite structure, and some a hydroxyl-depleted apatite structure. The results of this study are largely the same as those previously obtained for rat dentin. However, the relative amounts of the various phosphorus species in human and rat dentin are dramatically different. In particular, stoichiometric apatite is more abundant in human dentin than in rat dentin, whereas the converse is true for disordered-phase orthophosphates. Furthermore, spatial proximity among all phosphorus species in human dentin is identical within experimental error, in contrast to what observed for rat dentin. Although it is not clear how these spectroscopic data could relate to the hierarchical structure or the mechanical properties of teeth, our data reveal that the molecular structures of human and rat dentin at different growth stages are not exactly the same. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessArticle
Study on Paramagnetic Interactions of (CH3NH3)2CoBr4 Hybrid Perovskites Based on Nuclear Magnetic Resonance (NMR) Relaxation Time
Molecules 2019, 24(16), 2895; https://doi.org/10.3390/molecules24162895 - 09 Aug 2019
Cited by 3
Abstract
The thermal properties of organic–inorganic (CH3NH3)2CoBr4 crystals were investigated using differential scanning calorimetry and thermogravimetric analysis. The phase transition and partial decomposition temperatures were observed at 460 K and 572 K. Nuclear magnetic resonance (NMR) chemical [...] Read more.
The thermal properties of organic–inorganic (CH3NH3)2CoBr4 crystals were investigated using differential scanning calorimetry and thermogravimetric analysis. The phase transition and partial decomposition temperatures were observed at 460 K and 572 K. Nuclear magnetic resonance (NMR) chemical shifts depend on the local field at the site of the resonating nucleus. In addition, temperature-dependent spin–lattice relaxation times (T) were measured using 1H and 13C magic angle spinning NMR to elucidate the paramagnetic interactions of the (CH3NH3)+ cations. The shortening of 1H and 13C T of the (CH3NH3)2CoBr4 crystals are due to the paramagnetic Co2+ effect. Moreover, the physical properties of (CH3NH3)2CoBr4 with paramagnetic ions and those of (CH3NH3)2CdBr4 without paramagnetic ions are reported and compared. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Review

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Open AccessReview
Solid-State NMR Techniques for the Structural Characterization of Cyclic Aggregates Based on Borane–Phosphane Frustrated Lewis Pairs
Molecules 2020, 25(6), 1400; https://doi.org/10.3390/molecules25061400 - 19 Mar 2020
Cited by 1
Abstract
Modern solid-state NMR techniques offer a wide range of opportunities for the structural characterization of frustrated Lewis pairs (FLPs), their aggregates, and the products of cooperative addition reactions at their two Lewis centers. This information is extremely valuable for materials that elude structural [...] Read more.
Modern solid-state NMR techniques offer a wide range of opportunities for the structural characterization of frustrated Lewis pairs (FLPs), their aggregates, and the products of cooperative addition reactions at their two Lewis centers. This information is extremely valuable for materials that elude structural characterization by X-ray diffraction because of their nanocrystalline or amorphous character, (pseudo-)polymorphism, or other types of disordering phenomena inherent in the solid state. Aside from simple chemical shift measurements using single-pulse or cross-polarization/magic-angle spinning NMR detection techniques, the availability of advanced multidimensional and double-resonance NMR methods greatly deepened the informational content of these experiments. In particular, methods quantifying the magnetic dipole–dipole interaction strengths and indirect spin–spin interactions prove useful for the measurement of intermolecular association, connectivity, assessment of FLP–ligand distributions, and the stereochemistry of adducts. The present review illustrates several important solid-state NMR methods with some insightful applications to open questions in FLP chemistry, with a particular focus on supramolecular associates. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessReview
The Applications of Solid-State NMR to Conducting Polymers. The Special Case on Polyaniline
Molecules 2020, 25(3), 444; https://doi.org/10.3390/molecules25030444 - 21 Jan 2020
Cited by 1
Abstract
Polyaniline is one of the most well studied conducting polymers due to its advanced electrical, chemical, redox and morphological properties. The high conductivity of regular polyaniline, when partially oxidized and doped under acidic conditions, has been associated with the formation of unique electronic [...] Read more.
Polyaniline is one of the most well studied conducting polymers due to its advanced electrical, chemical, redox and morphological properties. The high conductivity of regular polyaniline, when partially oxidized and doped under acidic conditions, has been associated with the formation of unique electronic states known as polarons and bipolarons. Alternative aniline oxidation products and interesting nanotube and nanorod forms have been observed as the synthesis conditions are varied. Solid-state NMR has offered great opportunities for structural investigations and the determination of molecular dynamics in such a complex and diverse material. This review summarizes various applications of solid-state NMR techniques to polyaniline and its derivatives and the information that can be obtained by solid-state NMR. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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Open AccessFeature PaperReview
Solid State NMR: A Powerful Tool for the Characterization of Borophosphate Glasses
Molecules 2020, 25(2), 428; https://doi.org/10.3390/molecules25020428 - 20 Jan 2020
Cited by 1
Abstract
This review will show how solid state nuclear magnetic resonance (NMR) has contributed to a better understanding of the borophosphate glass structure. Over the last fifteen years, 1D and 2D magic angle spinning (MAS)-NMR has been used to produce key information about both [...] Read more.
This review will show how solid state nuclear magnetic resonance (NMR) has contributed to a better understanding of the borophosphate glass structure. Over the last fifteen years, 1D and 2D magic angle spinning (MAS)-NMR has been used to produce key information about both local and medium range organization in this type of glass. After a brief presentation on borophosphate glasses, the paper will focus on the description of the local order of phosphate and borate species obtained by 1D 31P-and 11B-MAS-NMR experiments, with a special emphasis on the improvements obtained at high magnetic fields on the borate speciation description. The last part of this review will show how correlation NMR provided new insights into the intermediate length scale order. Special attention will be paid to the quantitative data retrieved from 11B/31P REDOR-based NMR sequences and to the qualitative connectivity schemes observed on the 2D 11B/31P maps edited with the heteronuclear multiple quantum coherence (HMQC) NMR techniques. Full article
(This article belongs to the Special Issue Solid-State NMR Spectroscopy in Materials Chemistry)
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