Probing oxygen exchange between UiO-66(Zr) MOF and water using 17 O solid-state NMR.

The Zr-based Metal Organic Framework (MOF) UiO-66(Zr) is widely employed owing to its good thermal and chemical stabilities. Although the long-range structure of this MOF is preserved in the presence of water during several days, little is known about the formation of defects, which cannot be detected using diffraction techniques. We apply here 17 O solid-state NMR spectroscopy at 18.8 T to investigate the reactivity of UiO-66, through the exchange of oxygen atoms between the different sites of the MOF and water. For that purpose, we have selectively enriched in 17 O isotope the carboxylate groups of UiO-66(Zr) by using it with 17 O-labeled terephthalic acid prepared using mechanochemistry. In the presence of water at 50 °C and a following dehydration at 150 °C, we observe an overall exchange of O atoms between COO- and µ3 -O2- sites. Furthermore, we demonstrate that the three distinct oxygen sites, µ3 -OH, µ3 -O2- and COO- , of UiO-66(Zr) MOF can be enriched in 17 O isotope by post-synthetic hydrothermal treatment in the presence of 17 O-enriched water. These results demonstrate the lability of Zr-O bonds and the reactivity of UiO-66(Zr) with water.

PtII -N-Heterocyclic Carbene Complexes in Solvent-Free Alkene Hydrosilylation.

Herein, we report the catalytic activity of a series of platinum(II) pre-catalysts, bearing N-heterocyclic carbene (NHC) ligands, in the alkene hydrosilylation reaction. Their structural and electronic properties are fully investigated using X-ray diffraction analysis and nuclear magnetic resonance spectroscopy (NMR). Next, our study presents a structure-activity relationship within this group of pre-catalysts and gives mechanistic insights into the catalyst activation step. An exceptional catalytic performance of one of the complexes is observed, reaching a turnover number (TON) of 970 000 and a turnover frequency (TOF) of 40 417 h-1 at 1 ppm catalyst loading. Finally, an attractive solvent-free and open-to-air alkene hydrosilylation protocol, featuring efficient platinum removal (reduction of residual Pt from 582 ppm to 5.8 ppm), is disclosed.

Boron Adsorption Kinetics of Microcrystalline Cellulose and Polymer Resin.

Tailoring boron-polysaccharide interactions is an important strategy for developing functional soft materials such as hydrogels, fire retardants, and sorbents for environmental remediation, for example, using lignocellulosic biomass. For such applications to be realized, it is paramount to understand the adsorption kinetics of borate anions on cellulose and their local structures. Here, the kinetic aspects of boron adsorption by microcrystalline cellulose, lignin, and polymeric resin are investigated and compared. Borate anions interact with the vicinal diols in the glucopyranoside moieties of cellulose to yield chemisorbed boron chelate complexes. In contrast to cellulose, technical lignin contains fewer cis-vicinal diols, and it does not have a tendency to form such chelate complexes upon treatment with the aqueous boric acid solution. The formation kinetics and stability of these chelate complexes strongly depend on nanoscale structures, as well as reaction conditions such as pH and concentration of the sorbate and sorbent. Specifically, insights into the distinct boron adsorption sites were obtained by solid-state one-dimensional (1D) 11B magic-angle spinning NMR and the local structures and intermolecular interactions in the vicinities of boron chelate complexes are elucidated by analyzing two-dimensional (2D) 1H-13C and 11B-1H heteronuclear correlation NMR spectra. The total boron adsorption capacity of cellulose is estimated to be in the 1.3-3.0 mg range per gram of sorbent, which is lower than the boron adsorption capacity of a polystyrene-based resin, ∼17.2 mg of boron per gram of Amberlite IRA 743. Our study demonstrates that the local backbone and side chain flexibility as well as the structures of polyol groups play a significant role in determining the kinetic and thermodynamic stability of chelate complexes, yielding to different boron adsorption capabilities of lignocellulosic polymers.

Mechanochemical Synthesis and Study of the Local Structure of NaGaS2 Glass and Glass-Ceramics.

NaGaS2 is a newly discovered compound that has already shown great promise for a variety of applications because of its layered structure and ion exchange properties. In this work, crystalline NaGaS2 has been synthesized by an alternative method to what has been previously published, namely, by mechanochemistry, either by a direct one-step process or by a two-step process. In the one-step process, crystalline NaGaS2 is directly formed by milling sodium sulfide Na2S and gallium(III) sulfide Ga2S3. However, an amorphous material is present in majority together with the crystalline phase. In the two-step process, amorphous NaGaS2 is first obtained by mechanical milling and then heated above its glass transition temperature to obtain a glass-ceramic mainly composed of crystalline NaGaS2. For the two-step process, changes of the local atomic-level structure in amorphous NaGaS2 and after crystallization were analyzed by high-field solid-state nuclear magnetic resonance (NMR) spectroscopy as well as by X-ray total scattering and pair distribution function (PDF) analysis. Based on quantitative analysis on the 23Na NMR spectra, modifying the annealing treatment can promote the formation of the crystalline phase up to a molar fraction of 83.8%.

Indirect NMR detection via proton of nuclei subject to large anisotropic interactions, such as 14N, 195Pt, and 35Cl, using the T-HMQC sequence.

Recently, the T-hetero-nuclear multiple quantum coherence (T-HMQC) sequence using the TRAPDOR (transfer of population in double resonance) recoupling has been introduced for the indirect detection via protons of quadrupolar nuclei with spin I = 1 (14N) or 3/2 (35Cl) in solids at fast magic-angle spinning (MAS). The sequence is simple as it only uses four rectangular pulses and exhibits low t1-noise because the recoupling pulses are applied to the indirectly detected isotope, I. We demonstrate that this sequence is applicable for the detection via protons of spin-1/2 nuclei subject to large chemical shift anisotropy, such as 195Pt. We also report the proton detection of double-quantum (2Q) coherences of 14N nuclei using this sequence. This 2Q version is more robust to the adjustment of the magic angle and the instabilities of the MAS frequencies than its parent single-quantum (1Q) version since the 2Q coherences are not broadened by the first-order quadrupole interaction. In practice, than its 1Q counterpart for the indirect detection of 14N nuclei, the 2Q variant benefits from a slightly higher resolution and comparable sensitivity. In this article, we derive for the first time the Hamiltonian that describes the spin dynamics during the TRAPDOR recoupling. This Hamiltonian demonstrates the importance of the adiabaticity parameter as well as the role of third-order terms in the effective Hamiltonian. The effects of offsets, radio-frequency field, and recoupling time on the efficiency of the T-HMQC sequence are analyzed numerically as well as with experimental detection via protons of 195Pt nuclei in a mixture of cis- and trans-platin and that of 14N and 35Cl isotopes in l-histidine HCl.

Improved resolution for spin-3/2 isotopes in solids via the indirect NMR detection of triple-quantum coherences using the T-HMQC sequence.

The indirect NMR detection of quadrupolar nuclei in solids under magic-angle spinning (MAS) is possible with the through-space HMQC (heteronuclear multiple-quantum coherence) scheme incorporating the TRAPDOR (transfer of population in double-resonance) dipolar recoupling. This sequence, called T-HMQC, exhibits limited t1-noise. In this contribution, with the help of numerical simulations of spin dynamics, we show that most of the time, the fastest coherence transfer in the T-HMQC scheme is achieved when TRAPDOR recoupling employs the highest radiofrequency (rf) field compatible with the probe specifications. We also demonstrate how the indirect detection of the triple-quantum (3Q) coherences of spin-3/2 quadrupolar nuclei in solids improves the spectral resolution for these isotopes. The sequence is then called T-HMQC3. We demonstrate the gain in resolution provided by this sequence for the indirect proton detection of 35Cl nuclei in l-histidine∙HCl and l-cysteine∙HCl, as well as that of 23Na isotope in NaH2PO4. These experiments indicate that the gain in resolution depends on the relative values of the chemical and quadrupolar-induced shifts (QIS) for the different spin-3/2 species. In the case of NaH2PO4, we show that the transfer efficiency of the T-HMQC3 sequence employing an rf-field of 80 kHz with a MAS frequency of 62.5 kHz reaches 75% of that of the t1-noise eliminated (TONE) dipolar-mediated HMQC (D-HMQC) scheme.

Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15 N and 13 C Solid-State NMR.

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of 13 C NMR spectra and generally precludes the observation of 15 N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of 13 C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced 13 C NMR spectra indicate that the 13 C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of 15 N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.

Hadamard acquisition of 13 C-13 C 2-D correlation NMR spectra.

We show that a multiselective excitation with Hadamard encoding is a powerful tool for 2-D acquisition of 13 C─13 C homonuclear correlations. This method is not designed to improve the sensitivity, but rather to reduce the experiment time, provided there is sufficient sensitivity. Therefore, it allows fast acquisition of such 2-D spectra in labeled molecules. The technique has been demonstrated using a U─13 C─15 N histidine hydrochloride monohydrate sample allowing each point of the build-up curves of the 13 C─13 C cross-peaks to be recorded within 4 min 35 s, which is very difficult with conventional methods. Using the U─13 C─15 N f-MLF sample, we have demonstrated that the method can be applied to molecules with 14 13 C resonances with a minimum frequency separation of 240 Hz.

Efficient transfer of DNP-enhanced 1 H magnetization to half-integer quadrupolar nuclei in solids at moderate spinning rate.

We show herein how the proton magnetization enhanced by dynamic nuclear polarization (DNP) can be efficiently transferred at moderate magic-angle spinning (MAS) frequencies to half-integer quadrupolar nuclei, S ≥ 3/2, using the Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (D-RINEPT) technique, in which a symmetry-based SR 4 1 2 recoupling scheme built from adiabatic inversion 1 H pulses reintroduces the 1 H-S dipolar couplings, while suppressing the 1 H-1 H ones. The use of adiabatic pulses also improves the robustness to offsets and radiofrequency (rf)-field inhomogeneity. Furthermore, the efficiency of the polarization transfer is further improved by using 1 H composite pulses and continuous-wave irradiations between the recoupling blocks, as well as by manipulating the S satellite transitions during the first recoupling block. Furthermore, in the case of large 1 H-S dipolar couplings, the D-RINEPT variant with two pulses on the quadrupolar channel results in an improved transfer efficiency. We compare here the performances of this new adiabatic scheme with those of its parent version with single π pulses, as well as with those of PRESTO and CPMAS transfers. This comparison is performed using simulations as well as DNP-enhanced 27 Al, 95 Mo, and 17 O NMR experiments on isotopically unmodified γ-alumina, hydrated titania-supported MoO3 , Mg(OH)2 , and l-histidine·HCl·H2 O. The introduced RINEPT method outperforms the existing methods, both in terms of efficiency and robustness to rf-field inhomogeneity and offset.

On the use of radio-frequency offsets for improving double-quantum homonuclear dipolar recoupling of half-integer-spin quadrupolar nuclei.

Detecting proximities between nuclei is crucial for atomic-scale structure determination with nuclear magnetic resonance (NMR) spectroscopy. Different from spin-1/2 nuclei, the methodology for quadrupolar nuclei is limited for solids due to the complex spin dynamics under simultaneous magic-angle spinning (MAS) and radio-frequency irradiation. Herein, the performances of several homonuclear rotary recoupling (HORROR)-based homonuclear dipolar recoupling sequences are evaluated for 27 Al (spin-5/2). It is shown numerically and experimentally on mesoporous alumina that BR 2 2 1 outperforms the supercycled S3 sequence and its pure double-quantum (DQ) (bracketed) version, [S3 ], both in terms of DQ transfer efficiency and bandwidth. This result is surprising since the S3 sequence is among the best low-power recoupling schemes for spin-1/2. The superiority of BR 2 2 1 is thoroughly explained, and the crucial role of radio-frequency offsets during its spin dynamics is highlighted. The analytical approximation of BR 2 2 1 , derived in an offset-toggling frame, clarifies the interplay between offset and DQ efficiency, namely, the benefits of off-resonance irradiation and the trough in DQ efficiency for BR 2 2 1 when the irradiation is central between two resonances, both for spin-1/2 and half-integer-spin quadrupolar nuclei. Additionally, density matrix propagations show that the BR 2 2 1 sequence, applied to quadrupolar nuclei subject to quadrupolar interaction much larger than radio-frequency frequency field, can create single- and multiple-quantum coherences for near on-resonance irradiation. This significantly perturbs the creation of DQ coherences between central transitions of neighboring quadrupolar nuclei. This effect explains the DQ efficiency trough for near on-resonance irradiation, in the case of both cross-correlation and autocorrelation peaks. Overall, this work aids experimental acquisition of homonuclear dipolar correlation spectra of half-integer-spin quadrupolar nuclei and provides theoretical insights towards improving recoupling schemes at high magnetic field and fast MAS.

Through-space 11 B-27 Al correlation: Influence of the recoupling channel.

Through-space heteronuclear correlation (D-HETCOR) experiments based on heteronuclear multiple-quantum correlation (D-HMQC) and refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) sequences have been proven to be useful approaches for the detection of the spatial proximity between half-integer quadrupolar nuclei in solids under magic-angle spinning (MAS) conditions. The corresponding pulse sequences employ coherence transfers mediated by heteronuclear dipolar interactions, which are reintroduced under MAS by radiofrequency irradiation of only one of the two correlated nuclei. We investigate herein using numerical simulations of spin dynamics and solid-state NMR experiments on magnesium aluminoborate glass how the choice of the channel to which the heteronuclear dipolar recoupling is applied affects the transfer efficiency of D-HMQC and D-RINEPT sequences between 11 B and 27 Al nuclei. Experimental results show that maximum transfer efficiency is achieved when the recoupling scheme is applied to the channel, for which the spin magnetization is parallel to the B0 axis in average.

Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy.

We introduce a novel NMR approach that extends the capabilities of indirect dynamic nuclear polarization (DNP) under magic-angle spinning to probe the local environment of half-integer spin quadrupolar nuclei. Compared to cross-polarization, this novel method based on the refocused INEPT scheme with adiabatic dipolar recoupling is easier to optimize and does not distort the quadrupolar line shapes. Furthermore, the use of this technique, instead of the PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order) scheme or direct DNP, greatly improves the sensitivity of DNP-NMR for the detection of quadrupolar isotopes with small dipolar couplings to protons, including notably those located in the subsurface of inorganic materials or with low gyromagnetic ratio (γ). This technique has been applied to identify the atomic-level structure of Brønsted acid sites of hydrated titania-supported MoO3, MoO3/TiO2, a widely used heterogeneous catalyst. The spectra of protonated and unprotonated 17O sites, acquired in natural abundance, indicate the presence of various oxomolybdate species as well as HOMo2 and HOMo3 Brønsted acid sites. The enhanced sensitivity of this new method has also enabled the acquisition of the first DNP-enhanced spectra of 95Mo and 47,49Ti low-γ quadrupolar isotopes. This possibility has been demonstrated by detecting the signals of these nuclei near the surface of MoO3/TiO2. This technique has allowed the observation of 49Ti surface sites, which are absent from the bulk region of TiO2. Furthermore, both 95Mo and 47,49Ti DNP spectra have shown an increased structural disorder of TiO2 and MoO3 phases near the surface of the particles and notably the preferential location of the amorphous TiO2 phase at the surface of the particles. The proposed polarization transfer is also employed to acquire the first DNP-enhanced spectrum of 67Zn, another low-γ quadrupolar isotope. This possibility is demonstrated for Al-doped ZnO nanoparticles used in optoelectronic devices. The obtained 17O, 27Al, and 67Zn DNP-NMR data prove that the surface region of these nanoparticles contains ZnO phase as well as secondary phases, such as α-Al2O3 and partially inverse ZnAl2O4 spinel.

Quantification of the amount of mobile components in intact stratum corneum with natural-abundance 13C solid-state NMR.

The outermost layer of the skin is the stratum corneum (SC), which is mainly comprised of solid proteins and lipids. Minor amounts of mobile proteins and lipids are crucial for the macroscopic properties of the SC, including softness, elasticity and barrier function. Still this minor number of mobile components are not well characterized in terms of structure or amount. Conventional quantitative direct polarization (Q-DP) 13C solid-state NMR gives signal amplitudes proportional to concentrations, but fails to quantify the SC mobile components because of spectral overlap with the overwhelming signals from the solids. Spectral editing with the INEPT scheme suppresses the signals from solids, but also modulates the amplitudes of the mobile components depending on their values of the transverse relaxation times T2, scalar couplings JCH, and number of covalently bound hydrogens nH. This study describes a quantitative INEPT (Q-INEPT) method relying on systematic variation of the INEPT timing variables to estimate T2, JCH, nH, and amplitude for each of the resolved resonances from the mobile components. Q-INEPT is validated with a series of model systems containing molecules with different hydrophobicity and dynamics. For selected systems where Q-DP is applicable, the results of Q-INEPT and Q-DP are similar with respect to the linearity and uncertainty of the obtained molar ratios. Utilizing a reference compound with known concentration, we quantify the concentrations of mobile lipids and proteins within the mainly solid SC. By melting all lipids at high temperature, we obtain the total lipid concentration. These Q-INEPT results are the first steps towards a quantitative understanding of the relations between mobile component concentrations and SC macroscopic properties.

gem-Diol-Type Intermediate in the Activation of a Ketone on Sn-ß Zeolite as Studied by Solid-State NMR Spectroscopy.

Lewis acid zeolites have found increasing application in the field of biomass conversion, in which the selective transformation of carbonyl-containing molecules is of particular importance due to their relevance in organic synthesis. Mechanistic insight into the activation of carbonyl groups on Lewis acid sites is challenging and critical for the understanding of the catalytic process, which requires the identification of reaction intermediates. Here we report the observation of a stable surface gem-diol-type species in the activation of acetone on Sn-ß zeolite. 13 C, 119 Sn, and 13 C-119 Sn double-resonance NMR spectroscopic studies demonstrate that only the open Sn site ((SiO)3 Sn-OH) on Sn-ß is responsible for the formation of the surface species. 13 C MAS NMR experiments together with density functional theory calculations suggest that the gem-diol-type species exhibits high reactivity and can serve as an active intermediate in the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction of acetone with cyclohexanol. The gem-diol-type species offers an energy-preferable pathway for the direct carbon-to-carbon hydrogen transfer between ketone and alcohol. The results provide new insights into the transformation of carbonyl-containing molecules catalyzed by Lewis acid zeolites.

Improved sensitivity and quantification for 29Si NMR experiments on solids using UDEFT (Uniform Driven Equilibrium Fourier Transform).

We demonstrate the possibility to use UDEFT (Uniform Driven Equilibrium Fourier Transform) technique in order to improve the sensitivity and the quantification of one-dimensional 29Si NMR experiments under magic-angle spinning (MAS). We derive an analytical expression of the signal-to-noise ratios of UDEFT and single-pulse (SP) experiments subsuming the contributions of transient and steady-state regimes. Using numerical spin dynamics simulations and experiments on 29Si-enriched amorphous silica and borosilicate glass, we show that 59180298059180 refocusing composite π-pulse and the adiabatic inversion using tanh/tan modulation improve the robustness of UDEFT technique to rf-inhomogeneity, offset, and chemical shift anisotropy. These pulses combined with a two-step phase cycle limit the pulse imperfections and the artifacts produced by stimulated echoes. The sensitivity of SP, UDEFT and CPMG (Carr-Purcell-Meiboom-Gill) techniques are experimentally compared on functionalized and non-functionalized mesoporous silica. Furthermore, experiments on a flame retardant material prove that UDEFT technique provides a better quantification of 29Si sites with higher sensitivity than SP method.

Analysis of HMQC experiments applied to a spin ½ nucleus subject to very large CSA.

The acquisition of solid-state NMR spectra of "heavy" spin I = 1/2 nuclei, such as 119Sn, 195Pt, 199Hg or 207Pb can often prove challenging due to the presence of large chemical shift anisotropy (CSA), which can cause significant broadening of spectral lines. However, previous publications have shown that well-resolved spectra can be obtained via inverse 1H detection using HMQC experiments in combination with fast magic angle spinning. In this work, the efficiencies of different 195Pt excitation schemes are analyzed using SIMPSON numerical simulations and experiments performed on cis- and transplatin samples. These schemes include: hard pulses (HP), selective long pulses (SLP) and rotor-synchronized DANTE trains of pulses. The results show that for spectra of species with very large CSA, HP is little efficient, but that both DANTE and SLP provide efficient excitation profiles over a wide range of CSA values. In particular, it is revealed that the SLP scheme is highly robust to offset, pulse amplitude and length, and is simple to set up. These factors make SLP ideally suited to widespread use by "non-experts" for carrying out analyses of materials containing "heavy" spin I = 1/2 nuclei that are subject to very large CSAs. Finally, the existence of an "intermediate" excitation regime, with an rf-field strength in between those of HP and SLP, which is effective for large CSA, is demonstrated. It must be noted that in some samples, multiple sites may exist with very different CSAs. This is the case for 195Pt species with either square-planar or octahedral structures, with large or small CSA, respectively. These two types of CSAs can only be excited simultaneously with DANTE trains, which scale up the effective rf-field. Another way to obtain all the information is to perform two different experiments: one with SLP and the second with HP to excite the sites with moderate/large and small/moderate CSAs, respectively. These two complementary experiments, recorded with two different spinning speeds, can also be used to discriminate the center-band resonances from the spinning sidebands.

Recent developments in MAS DNP-NMR of materials.

Solid-state NMR spectroscopy is a powerful technique for the characterization of the atomic-level structure and dynamics of materials. Nevertheless, the use of this technique is often limited by its lack of sensitivity, which can prevent the observation of surfaces, defects or insensitive isotopes. Dynamic Nuclear Polarization (DNP) has been shown to improve by one to three orders of magnitude the sensitivity of NMR experiments on materials under Magic-Angle Spinning (MAS), at static magnetic field B0 ≥ 5 T, conditions allowing for the acquisition of high-resolution spectra. The field of DNP-NMR spectroscopy of materials has undergone a rapid development in the last ten years, spurred notably by the availability of commercial DNP-NMR systems. We provide here an in-depth overview of MAS DNP-NMR studies of materials at high B0 field. After a historical perspective of DNP of materials, we describe the DNP transfers under MAS, the transport of polarization by spin diffusion and the various contributions to the overall sensitivity of DNP-NMR experiments. We discuss the design of tailored polarizing agents and the sample preparation in the case of materials. We present the DNP-NMR hardware and the influence of key experimental parameters, such as microwave power, magnetic field, temperature and MAS frequency. We give an overview of the isotopes that have been detected by this technique, and the NMR methods that have been combined with DNP. Finally, we show how MAS DNP-NMR has been applied to gain new insights into the structure of organic, hybrid and inorganic materials with applications in fields, such as health, energy, catalysis, optoelectronics etc.

14N overtone nuclear magnetic resonance of rotating solids.

By irradiating and observing at twice the 14N Larmor frequency, overtone (OT) nuclear magnetic resonance (NMR) is capable of obtaining 14NOT spectra without first-order quadrupolar broadening. Direct excitation and detection of the usually "forbidden" double-quantum transition is mediated by the perturbation from the large quadrupole interaction to the spin states quantized by the Zeeman interaction. A recent study [L. A. O'Dell and C. I. Ratcliffe, Chem. Phys. Lett. 514, 168 (2011)] has shown that 14NOT NMR under magic-angle spinning (MAS) can yield high-resolution spectra with typical second-order quadrupolar line shapes allowing the measurement of 14N chemical shift and quadrupolar coupling parameters. This article has also shown that under MAS the main 14NOT peak is shifted by twice the sample spinning frequency with respect to its static position. We present the theory of 14NOT NMR of static or rotating samples and the physical picture of the intriguing spinning-induced shift in the second case. We use perturbation theory for the case of static samples and Floquet theory for rotating samples. In both cases, the results can be described by a so-called OT parameter that scales down the 14NOT radio-frequency (rf) excitation and signal detection. This OT parameter shows that the components of the rf field, which are transverse and longitudinal with respect to the magnetic field, are both effective for 14NOTrf excitation and signal detection. In the case of MAS at angular frequency ωr , the superposition of the excitation and detection components in the OT parameter makes either the +2ωr or -2ωr term the dominant 14NOT signal, depending on the sense of sample spinning with respect to the magnetic field. This leads to an apparent 14NOT signal shifted at twice the spinning frequency. The features of 14NOT NMR spectra for both static and rotating samples are illustrated with simulations. The spinning induced shift and its dependence on the spinning direction are confirmed experimentally by reversing the spinning direction and the field of the 36 T series-connected hybrid magnet at the US National High Magnetic Field Laboratory.

Observation of proximities between spin-1/2 and quadrupolar nuclei in solids: Improved robustness to chemical shielding using adiabatic symmetry-based recoupling.

We introduce a novel heteronuclear dipolar recoupling based on the R21-1 symmetry, which uses the tanh/tan (tt) shaped pulse as a basic inversion element and is denoted R21-1(tt). Using first-order average Hamiltonian theory, we show that this sequence is non-γ-encoded and that it reintroduces the |m| = 1 spatial component of the Chemical Shift Anisotropy (CSA) of the irradiated isotope and its heteronuclear dipolar interactions. Using numerical simulations and one-dimensional (1D) 27Al-{31P} through-space D-HMQC (Dipolar Heteronuclear Multiple-Quantum Correlation) experiments on VPI-5, we compare the performances of this recoupling to those of other non-γ-encoded |m| = 1 heteronuclear recoupling schemes: REDOR (Rotational-Echo DOuble Resonance), SFAM (Simultaneous Frequency and Amplitude Modulation) and R42-1(tt). Such comparison indicates that the R21-1(tt) scheme is more robust to CSA, offset and radiofrequency field inhomogeneities than the other schemes. We take advantage of the high robustness of R21-1(tt) to CSA and offset to demonstrate the possibility to correlate the signals of 207Pb isotope with those of neighboring half-integer spin quadrupolar nuclei. Such approach is demonstrated experimentally by acquiring 11B-{207Pb} D-HMQC 2D spectra of Pb4O(BO3)2 crystalline powder.

Solid-State NMR Spectroscopy Proves the Presence of Penta-coordinated Sc Sites in MIL-100(Sc).

Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45 Sc NMR experiment allows their specific observation in activated Sc3 BTB2 (H3 BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13 C-45 Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised.