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The addition of 17 OH 2 to silica at room temperature leads to spontaneous hydroxyl oxygen exchange and the selective isotopic enrichment of silanols, as observed using in and ex situ 17 O NMR. The discovery that silanols are labile alters our understanding of the chemistry of silica surfaces.

Materials with well-defined surfaces are drawing increased attention for the design of bespoke catalysts and nanomaterials. Gaining a detailed understanding of the surfaces of these materials is an important challenge, which is often complicated by surface polymorphism and dynamic restructuring. We introduce the use of surface-enhanced NMR spectroscopy for the observation of such surfaces, focusing on LaScO 3 as an example. We show that double-resonance NMR experiments correlating surface oxygen and probe molecules to the 139 La and 45 Sc nuclei at the surface reveal the material to be terminated by a ScO x monolayer. Surface-selective 17 O and 45 Sc NMR experiments further showed the material to be hydroxyl terminated and that the surface may be prone to dynamic restructuring as a result of moisture exposure. Perhaps most interestingly, surface-selective 139 La NMR experiments revealed the existence of previously undetected surface lanthanum defects, suggesting that surface-enhanced NMR may be useful as a guide in the synthesis of defect-free surfaces in the design of various nanomaterials.

Motionally averaged dipolar couplings are an important tool for understanding the complex dynamics of catalysts, polymers, and biomolecules. While there is a plethora of solid-state NMR pulse sequences available for their measurement, in can be difficult to gauge the methods' strengths and weaknesses. In particular, there has not been a comprehensive comparison of their performance in natural abundance samples, where 1 H homonuclear dipolar couplings are important and the use of large MAS rotors may be required for sensitivity reasons. In this work, we directly compared some of the more common methods for measuring C-H dipolar couplings in natural abundance samples using L-alanine (L-Ala) and the N-formyl-L-methionyl-L-leucyl-L-phenylalanine (fMLF) tripeptide as model systems. We evaluated their performance in terms of accuracy, resolution, sensitivity, and ease of implementation. We found that, despite the presence of 1 H homonuclear dipolar interactions, all methods, with the exception of REDOR, were able to yield the reasonable dipolar coupling strengths for both mobile and static moieties. Of these methods, PDLF provides the most convenient workflow and precision at the expense of low sensitivity. In low-sensitivity cases, MAS-PISEMA and DIPSHIFT appear to be the better options., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

1 H solid-state NMR spectra are plagued by low resolution, necessitating the use of complex pulse sequences or specialized equipment. We introduce a new resolution enhancement method, inspired by super-resolution microscopy, that uses a 2D Hahn-echo experiment to constrain deconvolution. The result is an effective doubling of the MAS frequency.

The NMR lineshapes produced by half-integer quadrupolar nuclei are sensitive to 11 distinct fit parameters per inequivalent site. To date, automatic fitting routines have failed to replace manual parameter insertion and evaluation due to the importance of local minima and the need for fitting multiple-field magic-angle spinning (MAS) and static spectra simultaneously. Herein we introduce a new tool, AMES-Fit (Automatic Multiple Experiment Simulation and Fitting), to automatically find the global best-fit simulation parameters for a series of multiple-field NMR lineshapes. AMES-Fit uses an adaptive step size random search algorithm to dynamically probe parameter space and requires minimal human input. The best fits are obtained in a few minutes of computation time that would otherwise have required several person-hours of work. The program is freely available and open-source., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Mesoporous silicon nitride (Si 3 N 4 ) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal-ligand orbital overlap. Here, tetrabenzyl zirconium (ZrBn 4 ) was chemisorbed on Si 3 N 4 , and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C-H bond activation along the Zr-N bond, this material was found to be a highly active (1.53 mol propene mol Zr -1 h -1 at 450 °C) and selective (99% to propylene) catalyst for propane dehydrogenation. In contrast, the homologous silica supported complex exhibited negligible activity under these conditions.

The past few decades have seen tremendous growth in the area of single-site heterogeneous catalysis, which aims to combine the best aspects of homogeneous and heterogeneous catalysis, namely molecular-level site control and ease of separation/recycling. Despite this, we still do not have a means of assessing site homogeneity and whether the produced catalyst is indeed a "single-site". Recent developments have enabled the use of NMR-based distance measurements to determine the conformations and configurations of surface sites, leading to the question whether such measurements can be used to distinguish materials containing either single or multiple surface sites with otherwise indistinguishable NMR properties. We describe a Monte Carlo-based multi-structure search algorithm and its application to the determination of multi-site structures from supported metal complexes. The sensitivity of REDOR data to the existence of multiple sites is assessed using synthetic data and prior literature examples are revisited to determine whether the single-site approximation was indeed appropriate. We lastly apply this new methodology to differentiate the configurations of zirconocene complexes grafted onto alumina supports that were thermally treated at different temperatures.

Competing models exist to explain the differences in the activity of zeolites and amorphous silica-aluminas. Some postulate that silica-alumina contains dilute zeolitic bridging acid sites, while others favor a pseudo-bridging silanol model. We employed a selective isotope labeling strategy to assess the existence of Si-O(H)-Al bonds using NMR-based distance measurements.

The inertness of elemental selenium is a significant obstacle in the synthesis of selenium-containing materials at low reaction temperatures. Over the years, several recipes have been developed to overcome this hurdle; however, most of the methods are associated with the use of highly toxic, expensive, and environmentally harmful reagents. As such, there is an increasing demand for the design of cheap, stable, and nontoxic reactive selenium precursors usable in the low-temperature synthesis of transition metal selenides with vast applications in nanotechnology, thermoelectrics, and superconductors. Herein, a novel synthetic route has been developed for activating elemental selenium by using a solvothermal approach. By comprehensive 77 Se NMR, Raman, and infrared spectroscopies and gas chromatography-mass spectrometry, we show that the activated Se solution contained HSe - , [Se-Se] 2- , and Se 2- ions, as well as dialkyl selenide (R 2 Se) and dialkyl diselenide (R-Se-Se-R) species in dynamic equilibrium. This also corresponded to the first observation of naked Se 2 2- in solution. The versatility of the developed Se precursor was demonstrated by the successful synthesis of (i) the polycrystalline room-temperature modification of the β-Ag 2 Se thermoelectric material; (ii) large single crystals of superconducting β-FeSe; (iii) CdSe nanocrystals with different particle sizes (3-10 nm); (iv) nanosheets of PtSe 2 ; and (v) mono- and dibenzyl selenides and diselenides at room temperature. The simplicity and diversity of the developed Se activation method holds promise for applied and fundamental research.

The sensitivity of NMR spectroscopy is considerably enhanced by dynamic nuclear polarization (DNP). In DNP polarization is transferred from unpaired electrons of a polarizing agent to nearby proton spins. In solids, this transfer is followed by the transport of hyperpolarization to the bulk via 1 H- 1 H spin diffusion. The efficiency of these steps is critical to obtain high sensitivity gains, but the pathways for polarization transfer in the region near the unpaired electron spins are unclear. Here we report a series of seven deuterated and one fluorinated TEKPol biradicals to probe the effect of deprotonation on MAS DNP at 9.4 T. The experimental results are interpreted with numerical simulations, and our findings support that strong hyperfine couplings to nearby protons determine high transfer rates across the spin diffusion barrier to achieve short build-up times and high enhancements. Specifically, 1 H DNP build-up times increase substantially with TEKPol isotopologues that have fewer hydrogen atoms in the phenyl rings, suggesting that these protons play a crucial role transferring the polarization to the bulk. Based on this new understanding, we have designed a new biradical, NaphPol, which yields significantly increased NMR sensitivity, making it the best performing DNP polarizing agent in organic solvents to date., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Boron monoxide (BO), prepared by the thermal condensation of tetrahydroxydiboron, was first reported in 1955; however, its structure could not be determined. With the recent attention on boron-based two-dimensional materials, such as borophene and hexagonal boron nitride, there is renewed interest in BO. A large number of stable BO structures have been computationally identified, but none are supported by experiments. The consensus is that the material likely forms a boroxine-based two-dimensional material. Herein, we apply advanced 11 B NMR experiments to determine the relative orientations of B(B)O 2 centers in BO. We find that the material is composed of D 2 h -symmetric O 2 B-BO 2 units that organize to form larger B 4 O 2 rings. Further, powder diffraction experiments additionally reveal that these units organize to form two-dimensional layers with a random stacking pattern. This observation is in agreement with earlier density functional theory (DFT) studies that showed B 4 O 2 -based structures to be the most stable.

Colloidal chemistry holds promise to prepare uniform and size-controllable pre-catalysts; however, it remains a challenge to unveil the atomic-level transition from pre-catalysts to active catalytic surfaces under the reaction conditions to enable the mechanistic design of catalysts. Here, we report an ambient-pressure X-ray photoelectron spectroscopy study, coupled with in situ environmental transmission electron microscopy, infrared spectroscopy, and theoretical calculations, to elucidate the surface catalytic sites of colloidal Ni nanoparticles for CO 2 hydrogenation. We show that Ni nanoparticles with phosphine ligands exhibit a distinct surface evolution compared with amine-capped ones, owing to the diffusion of P under oxidative (air) or reductive (CO 2 + H 2 ) gaseous environments at elevated temperatures. The resulting NiP x surface leads to a substantially improved selectivity for CO production, in contrast to the metallic Ni, which favors CH 4 . The further elimination of surface metallic Ni sites by designing multi-step P incorporation achieves unit selectivity of CO in high-rate CO 2 hydrogenation.

The Overhauser effect in the dynamic nuclear polarization (DNP) of non-conducting solids has drawn much attention due to the potential for efficient high-field DNP as well as a general interest in the underlying principles that enable the Overhauser effect in small molecules. We recently reported the observation of 1H and 2H Overhauser effects in H3C- or D3C-functionalized Blatter radical analogs, which we presumed to be caused by methyl rotation. In this work, we look at the mechanism for methyl-driven Overhauser DNP in greater detail, considering methyl librations and tunneling in addition to classical rotation. We predict the temperature dependence of these mechanisms using density functional theory and spin dynamics simulations. Comparisons with results from ultralow-temperature magic angle spinning-DNP experiments revealed that cross-relaxation at temperatures above 60 K originates from both libration and rotation, while librations dominate at lower temperatures. Due to the zero-point vibrational nature of these motions, they are not quenched by very low temperatures, and methyl-driven Overhauser DNP is expected to increase in efficiency down to 0 K, predominantly due to increases in nuclear relaxation times., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Obtaining three-dimensional (3D) configurational information of surface organometallic complexes is a persistent challenge due to the low spatial sensitivity of most spectroscopic methods. We show that employing 17 O-enriched supports enables highly informative multidimensional NMR experiments, including radial and vertical distance measurements, that can be used to elucidate site geometry.

Catalytic C-H borylation is an attractive method for the conversion of the most abundant hydrocarbon, methane (CH 4 ), to a mild nucleophilic building block. However, existing CH 4 borylation catalysts often suffer from low turnover numbers and conversions, which is hypothesized to result from inactive metal hydride agglomerates. Herein we report that the heterogenization of a bisphosphine molecular precatalyst, [(dmpe)Ir(cod)CH 3 ], onto amorphous silica dramatically enhances its performance, yielding a catalyst that is 12-times more efficient than the current standard for CH 4 borylation. The catalyst affords over 2000 turnovers at 150 °C in 16 h with a selectivity of 91.5% for mono- vs diborylation. Higher catalyst loadings improve yield and selectivity for the monoborylated product (H 3 CBpin) with 82.8% yield and >99% selectivity being achieved with 1255 turnovers. X-ray absorption and dynamic nuclear polarization-enhanced solid-state NMR spectroscopic studies identify the supported precatalyst as an Ir I species, and indicate that upon completion of catalysis, multinuclear Ir polyhydrides are not formed. This is consistent with the hypothesis that immobilization of the organometallic Ir species on a surface prevents bimolecular decomposition pathways. Immobilization of the homogeneous Ir I fragment onto amorphous silica represents a unique and simple strategy to improve the TON and longevity of a CH 4 borylation catalyst.

Dynamics play significant roles in chemistry and biochemistry-molecular motions impact both large- and small-scale chemical reactions in addition to biochemical processes. In many systems, including heterogeneous catalysts, the characterization of dynamics remains a challenge. The most common approaches involve the solid-state NMR measurement of anisotropic interactions, in particular 2 H quadrupolar coupling and 1 H-X dipolar coupling, which generally require isotope enrichment. Due to the high sensitivity of 1 H NMR, 1 H chemical shift anisotropy (CSA) is a particularly enticing, and underexplored, dynamics probe. We carried out 1 H CSA and 1 H- 13 C dipolar coupling measurements in a series of model supported complexes to understand how 1 H CSA can be leveraged to gain dynamic information for heterogeneous catalysts. Mathematical descriptions are given for the dynamic averaging of the CSA tensor, and its dependence on orientation and asymmetry. The variability of the orientation of the tensor in the molecular frame, in addition to its magnitude and asymmetry, negatively impacts attempts to extract quantitative dynamic information. Nevertheless, 1 H CSA measurements can reveal useful qualitative insights into the motions of a particularly dilute site, such as from a surface species.

C-H/Et-Al exchange in zirconium-catalyzed reactions of saturated hydrocarbons and AlEt 3 affords versatile organoaluminum compounds and ethane. The grafting of commercially available Zr(O t Bu) 4 on silica/alumina gives monopodal ≡SiO-Zr(O t Bu) 3 surface pre-catalyst sites that are activated in situ by ligand exchange with AlEt 3 . The catalytic C-H alumination of dodecane at 150 °C followed by quenching in air affords n -dodecanol as the major product, revealing selectivity for methyl group activation. Shorter hydrocarbon or alcohol products were not detected under these conditions. Catalytic reactions of cyclooctane and AlEt 3 , however, afford ring-opened products, indicating that C-C bond cleavage occurs readily in methyl group-free reactants. This selectivity for methyl group alumination enables the C-H alumination of polyethylenes, polypropylene, polystyrene, and poly-α-olefin oils without significant chain deconstruction. In addition, the smallest hydrocarbon, methane, undergoes selective mono-alumination under solvent-free catalytic conditions, providing a direct route to Al-Me species.

The surface arrangement of motional organic functionalities is explored by experimental dipolar coupling measurements and the prediction of motionally-averaged coupling constant from molecular dynamics simulations. The use of machine learning potentials was key to reaching the timescale required. The distance between dynamic surface species are important in cooperative heterogeneous catalysis.

Due to their high gyromagnetic ratio, there is considerable interest in measuring distances and correlations involving protons, but such measurements are compounded by the simultaneous recoupling of chemical shift anisotropy (CSA). This secondary recoupling adds additional modulations to the signal intensities that ultimately lead to t 1 -noise and signal decay. Recently, Venkatesh et al. demonstrated that the addition of CSA refocusing periods during 1 H-X dipolar recoupling led to sequences with far higher stability and performance. Herein, we describe a related effort and develop a symmetry-based recoupling sequence that continually refocuses the 1 H CSA. This sequence shows superior performance to the regular and t 1 -noise eliminated D-HMQC sequences in the case of spin-1/2 nuclei and comparable performance to the later for half-integer quadrupoles., (Copyright © 2022 Elsevier Inc. All rights reserved.)

The Overhauser effect is unique among DNP mechanisms in that it requires the modulation of the electron-nuclear hyperfine interactions. While it dominates DNP in liquids and metals, where unpaired electrons are highly mobile, Overhauser DNP is possible in insulating solids if rapid structural modulations are linked to a modulation in hyperfine coupling. Herein, we report that Overhauser DNP can be triggered by the strategic addition of a methyl group, demonstrated here in a Blatter's radical. The rotation of the methyl group leads to a modulation of the hyperfine coupling to its protons, which in turn facilitates electron-nuclear cross-relaxation. Removal of the methyl protons, through deuteration, quenches the process, as does the reduction of the hyperfine coupling strength. This result suggests the possibility for the design of tailor-made Overhauser DNP polarizing agents for high-field MAS-DNP.

The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] (1). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4 % methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate., (© 2022 Wiley-VCH GmbH.)

Solid-state nuclear magnetic resonance can be enhanced using unpaired electron spins with a method known as dynamic nuclear polarization (DNP). Fundamentally, DNP involves ensembles of thousands of spins, a scale that is difficult to match computationally. This scale prevents us from gaining a complete understanding of the spin dynamics and applying simulations to design sample formulations. We recently developed an ab initio model capable of calculating DNP enhancements in systems of up to ∼1000 nuclei; however, this scale is insufficient to accurately simulate the dependence of DNP enhancements on radical concentration or magic angle spinning (MAS) frequency. We build on this work by using ab initio simulations to train a hybrid model that makes use of a rate matrix to treat nuclear spin diffusion. We show that this model can reproduce the MAS rate and concentration dependence of DNP enhancements and build-up time constants. We then apply it to predict the DNP enhancements in core-shell metal-organic-framework nanoparticles and reveal new insights into the composition of the particles' shells.

This is the first report of a multifunctional separator for potassium-metal batteries (KMBs). Double-coated tape-cast microscale AlF 3 on polypropylene (AlF 3 @PP) yields state-of-the-art electrochemical performance: symmetric cells are stable after 1000 cycles (2000 h) at 0.5 mA cm -2 and 0.5 mAh cm -2 , with 0.042 V overpotential. Stability is maintained at 5.0 mA cm -2 for 600 cycles (240 h), with 0.138 V overpotential. Postcycled plated surface is dendrite-free, while stripped surface contains smooth solid electrolyte interphase (SEI). Conventional PP cells fail rapidly, with dendrites at plating, and "dead metal" and SEI clumps at stripping. Potassium hexacyanoferrate(III) cathode KMBs with AlF 3 @PP display enhanced capacity retention (91% at 100 cycles vs 58%). AlF 3 partially reacts with K to form an artificial SEI containing KF, AlF 3 , and Al 2 O 3 phases. The AlF 3 @PP promotes complete electrolyte wetting and enhances uptake, improves ion conductivity, and increases ion transference number. The higher of K + transference number is ascribed to the strong interaction between AlF 3 and FSI - anions, as revealed through 19 F NMR. The enhancement in wetting and performance is general, being demonstrated with ester- and ether-based solvents, with K-, Na-, or Li- salts, and with different commercial separators. In full batteries, AlF 3 prevents Fe crossover and cycling-induced cathode pulverization., (© 2021 Wiley-VCH GmbH.)

The immobilization of molecularly precise metal complexes to substrates, such as silica, provides an attractive platform for the design of active sites in heterogeneous catalysts. Specific steric and electronic variations of the ligand environment enable the development of structure-activity relationships and the knowledge-driven design of catalysts. At present, however, the three-dimensional environment of the precatalyst, much less the active site, is generally not known for heterogeneous single-site catalysts. We explored the degree to which NMR-based surface-to-complex interatomic distances could be used to solve the three-dimensional structures of three silica-supported metal complexes. The structure solution revealed unexpected features related to the environment around the metal that would be difficult to discern otherwise. This approach appears to be highly robust and, due to its simplicity, is readily applied to most single-site catalysts with little extra effort.

An innovative method of synthesis is reported for the large and diverse (RE) 6 (TM) x (Tt) 2 S 14 (RE = rare-earth, TM = transition metals, Tt = Si, Ge, and Sn) family of compounds (∼1000 members, ∼325 contain Si), crystallizing in the noncentrosymmetric, chiral, and polar P 6 3 space group. Traditional synthesis of such phases involves the annealing of elements or binary sulfides at elevated temperatures. The atomic mixing of refractory components technique, presented here, allows the synthesis of known members and vastly expands the family to nearly the entire transition metal block, including 3d, 4d, and 5d TMs with oxidation states ranging from 1+ to 4+. Arc-melting of the RE, TM, and tetrel elements of choice forms an atomically-mixed precursor, which readily reacts with sulfur providing bulk powders and large single crystals of the target quaternary sulfides. Detailed in situ and ex situ experiments show the mechanism of formation, which involves multiphase binary sulfide intermediates. Crystal structures and metal oxidation states were corroborated by a combination of single crystal X-ray diffraction, elemental analysis, EPR, NMR, and SQUID magnetometry. The potential of La 6 (TM) x (Tt) 2 S 14 compounds for non-linear optical applications was also demonstrated., Competing Interests: Authors declare no conflict of interests., (This journal is © The Royal Society of Chemistry.)

Orientationally-dependent interactions such as dipolar coupling, quadrupolar coupling, and chemical shift anisotropy (CSA) contain a wealth of spatial information that can be used to elucidate molecular conformations and dynamics. To determine the sign of the chemical shift tensor anisotropy parameter (δ aniso ), both the |m| ​= ​1 and |m| ​= ​2 components of the CSA need to be symmetry allowed, while the recoupling of the |m| ​= ​1 term is accompanied with the reintroduction of homonuclear dipolar coupling components. Therefore, previously suggested sequences which solely recouple the |m| ​= ​2 term cannot determine the sign a 1 H's δ aniso in a densely-coupled network. In this study, we demonstrate the CSA recoupling of strongly dipolar coupled 1 H spins using the Cn n 1 (90 0 360 180 540 0 360 180 90 0 ) sequence. This pulse scheme recouples both the |m| ​= ​1 and |m| ​= ​2 CSA terms but the scaling factors for the homonuclear dipolar coupling terms are zeroed. Consequently, the sequence is sensitive to the sign of δ aniso but is not influenced by homonuclear dipolar interactions., Competing Interests: Declaration of competing interest The authors declare that they have not known conflicting financial interests or personal relationships that could have appeared to influence the work reported in this study., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Constant-time (CT) dipolar heteronuclear multiple quantum coherence (D-HMQC) has previously been demonstrated as a method for proton detection of high-resolution wideline NMR spectra of spin-1/2 nuclei with large chemical shift anisotropy (CSA). However, 1 H transverse relaxation and t 1 -noise often reduce the sensitivity of D-HMQC experiments, preventing the theoretical gains in sensitivity provided by 1 H detection from being realized. Here we demonstrate a series of improved pulse sequences for 1 H detection of spin-1/2 nuclei under fast MAS, with 195 Pt SSNMR experiments on cisplatin as an example. First, a t 1 -incrementation protocol for D-HMQC dubbed Arbitrary Indirect Dwell (AID) is demonstrated. AID allows the use of arbitrary, rotor asynchronous t 1 -increments, but removes the constant time period from CT D-HMQC, resulting in improved sensitivity by reducing transverse relaxation losses. Next, we show that short high-power adiabatic pulses (SHAPs), which efficiently invert broad MAS sideband manifolds, can be effectively incorporated into 1 H detected symmetry-based resonance echo double resonance (S-REDOR) and t 1 -noise eliminated (TONE) D-HMQC experiments. The S-REDOR experiments with SHAPs provide approximately double the dipolar dephasing, as compared to experiments with rectangular inversion pulses. We lastly show that sensitivity and resolution can be further enhanced with the use of swept excitation pulses as well as adiabatic magic angle turning (aMAT)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Complex polymorphic relationships in the LnSiP3 (Ln = La and Ce) family of compounds are reported. An innovative synthetic method was developed to overcome differences in the reactivities of the rare-earth metal and refractory silicon with phosphorus. Reactions of atomically mixed Ln + Si with P allowed for selective control over the reaction outcomes resulting in targeted isolation of three new polymorphs of LaSiP3 and two polymorphs of CeSiP3. In situ X-ray diffraction studies revealed that the developed method bypasses formation of the thermodynamic dead-end, the binary SiP. Careful re-determination of the crystal structure ruled out the previously reported ordered centrosymmetric structure of CeSiP3 and showed that the main LnSiP3 polymorphs crystallize in the non-centrosymmetric Pna21 and Aea2 space groups featuring distinct distortions of the regular P square net to yield either cis-trans 1D phosphorus chains (Pna21) or disordered-2D phosphorus layers (Aea2). The disordered 2D nature of the P layers in the Aea2 LaSiP3 polymorph was confirmed by Raman spectroscopy. A unique centrosymmetric P21/c polymorph was observed for LaSiP3 and has a completely different crystal structure lacking P layers. Consecutive polymorphic transformations at increasing temperatures for LaSiP3(Pna21 → P21/c → Aea2) were derived from optimized synthetic profiles and confirmed by a combination of phonon computations and experimental in situ and ex situ annealings. Crystal structures of the LaSiP3 polymorphs were verified via advanced solid state NMR analysis using 31P MAS and 31P{139La} double resonance techniques. A combination of phonon and electronic structure calculations, NMR T1 relaxation times, UV/Vis/NIR spectroscopy, and resistivity measurements revealed that all the reported polymorphs are semiconductors with resistivities and thermal conductivities strongly dependent on the degree of distortion of P square layers in the crystal structure. Reported here, non-centrosymmetric LnSiP3 polymorphs with tunable resistivity and thermal conductivity provide a platform for the development of novel functional materials with a wide range of applications.

Despite the growing number of successful applications of dynamic nuclear polarization (DNP)-enhanced magic-angle spinning (MAS) NMR in structural biology and materials science, the nuclear polarizations achieved by current MAS DNP instrumentation are still considerably lower than the theoretical maximum. The method could be significantly strengthened if experiments were performed at temperatures much lower than those currently widely used (∼100 K). Recently, the prospects of helium (He)-cooled MAS DNP have been increased with the instrumental developments in MAS technology that uses cold helium gas for sample cooling. Despite the additional gains in sensitivity that have been observed with He-cooled MAS DNP, the performance of the technique has not been evaluated in the case of surfaces and interfaces that benefit the most from DNP. Herein, we studied the efficiency of DNP at temperatures between ∼30 K and ∼100 K for organically functionalized silica material and a homogeneous solution of small organic molecules at a magnetic field B0 = 16.4 T. We recorded the changes in signal enhancement, paramagnet-induced quenching and depolarization effects, DNP build-up rate, and Boltzmann polarization. For these samples, the increases in MAS-induced depolarization and DNP build-up times at around 30 K were not as severe as anticipated. In the case of the surface species, we determined that MAS DNP at 30 K provided ∼10 times higher sensitivity than MAS DNP at 90 K, which corresponds to the acceleration of experiments by multiplicative factors of up to 100.

γ-encoded recoupling sequences are known to produce strong amplitude modulations that lead to sharp doublets when Fourier transformed. These doublets depend very little on the recoupled tensor asymmetry and thus enable for the straightforward determination of dynamic order parameters. It can, however, be difficult to measure small anisotropies, or small order parameters, using such sequences; the resonances from the doublet may overlap with each other, or with the zero-frequency glitch. This limitation has prevented the widespread use of 1 H chemical shift anisotropy (CSA) for the measurement of dynamics, particularly for CH protons which typically have CSAs of only a few ppm when immobile. Here, we introduce a simple modification to the traditional 1 H CSA and proton-detected local field pulse sequences that enables the acquisition of a hypercomplex dataset and the removal of the uncorrelated magnetization that results in the zero-frequency glitch. These new sequences then yield a frequency shift in the indirect dimension, rather than a splitting, which is easily identifiable even in cases of weak interactions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Dynamic nuclear polarization (DNP) and indirect detection are two commonly applied approaches for enhancing the sensitivity of solid-state NMR spectroscopy. However, their use in tandem has not yet been investigated. With the advent of low-temperature fast magic angle spinning (MAS) probes with 1.3-mm diameter rotors capable of MAS at 40 ​kHz it becomes feasible to combine these two techniques. In this study, we performed DNP-enhanced 2D indirectly detected heteronuclear correlation (idHETCOR) experiments on 13 C, 15 N, 113 Cd and 89 Y nuclei in functionalized mesoporous silica, CdS nanoparticles, and Y 2 O 3 nanoparticles. The sensitivity of the 2D idHETCOR experiments was compared with those of DNP-enhanced directly-detected 1D cross polarization (CP) and 2D HETCOR experiments performed with a standard 3.2-mm rotor. Due to low CP polarization transfer efficiencies and large proton linewidth, the sensitivity gains achieved by indirect detection alone were lower than in conventional (non-DNP) experiments. Nevertheless, despite the smaller sample volume the 2D idHETCOR experiments showed better absolute sensitivities than 2D HETCOR experiments for nuclei with the lowest gyromagnetic ratios. For 89 Y, 2D idHETCOR provided 8.2 times better sensitivity than the 1 D 89 Y-detected CP experiment performed with a 3.2-mm rotor., Competing Interests: Declaration of competing interest ZW, MPH, TK, FAP, YC, AJR, and MP declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. FE, CR, and AP work for the Bruker Biospin Corporation which has developed and commercialized the fast-MAS probehead investigated in this study. This relationship has not impacted the analysis of the work presented here., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Heteronuclear correlation (HETCOR) spectroscopy is one of the key tools in the arsenal of the solid-state NMR spectroscopist to probe chemical and spatial proximities between two different nuclei and enhance spectral resolution. Dipolar heteronuclear multiple-quantum coherence (D-HMQC) is a powerful technique that can be potentially utilized to obtain 1H detected 2D HETCOR solid-state NMR spectra of any NMR active nucleus. A long-standing problem in 1H detected D-HMQC solid-state NMR experiments is the presence of t1-noise which reduces sensitivity and impedes spectral interpretation. In this contribution, we describe novel pulse sequences, termed t1-noise eliminated (TONE) D-HMQC, that minimize t1-noise and can provide higher sensitivity and resolution than conventional D-HMQC. Monte-Carlo and numerical simulations confirm that t1-noise in conventional D-HMQC primarily occurs because random MAS frequency fluctuations cause variations in the NMR signal amplitude from scan to scan, leading to imperfect cancellation of uncorrelated signals by phase cycling. The TONE D-HMQC sequence uses 1H π-pulses to refocus the evolution of 1H CSA across each SR421 recoupling block, improving the stability of the pulse sequence to random MAS frequency fluctuations. The 1H refocusing pulses also restore the orthogonality of in-phase and anti-phase magnetization for all crystallite orientations at the end of each recoupling block, enabling the use of 90° flip-back or LG spin-lock trim pulses to reduce the intensity of uncorrelated signals. We demonstrate the application of these methods to acquire 1H detected 2D 1H{35Cl} and 1H{13C} HETCOR spectra of histidine·HCl·H2O with reduced t1-noise. To show generality, we also apply these methods to obtain 2D 1H{17O} spectra of 20%-17O fmoc-alanine and for the first time at natural abundance, 2D 1H{25Mg} HETCOR spectra of magnesium hydroxide. The TONE D-HMQC sequences are also used to probe 1H-25Mg and 1H-27Al proximities in Mg-Al layered double hydroxides and confirm the even mixing of Mg and Al in these materials.

Theoretical models aimed at describing magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) NMR have great potential in facilitating the in silico design of DNP polarizing agents and formulations. These models must typically face a trade-off between the accuracy of a strict quantum mechanical description and the need for using realistically large spin systems, for instance, using phenomenological models. Here, we show that the use of aggressive state-space restrictions and an optimization strategy allows full-scale ab initio MAS-DNP simulations of spin systems containing thousands of nuclei. Our simulations are shown to reproduce experimental DNP enhancements quantitatively, including their MAS rate dependence, for both frozen solutions and solid materials. They also reveal the importance of a previously unrecognized structural feature found in some polarizing agents that helps minimize the sensitivity losses imposed by the spin diffusion barrier.

Cesium lead halide perovskite quantum dots (QDs) have gained significant attention as next-generation optoelectronic materials; however, their properties are highly dependent on their surface chemistry. The surfaces of cuboidal CsPbBr 3 QDs have been intensively studied by both theoretical and experimental techniques, but fundamental questions still remain about the atomic termination of the QDs. The binding sites and modes of ligands at the surface remain unproven. Herein, we demonstrate that solid-state NMR spectroscopy allows the unambiguous assignment of organic surface ligands via 1 H, 13 C, and 31 P NMR. Surface-selective 133 Cs solid-state NMR spectra show the presence of an additional 133 Cs NMR signal with a unique chemical shift that is attributed to Cs atoms terminating the surface of the particle and which are likely coordinated by carboxylate ligands. Dipolar dephasing curves that report on the distance between the surface ammonium ligands and Cs and Pb were recorded using double resonance 1 H{ 133 Cs} RESPDOR and 1 H{ 207 Pb} S-REDOR experiments. Model QD surface slabs with different possible surface terminations were generated from the CsPbBr 3 crystal structure, and theoretical dipolar dephasing curves considering all possible 1 H- 133 Cs/ 207 Pb spin pairs were then calculated. Comparison of the calculated and experimental dephasing curves indicates the particles are CsBr terminated (not PbBr 2 terminated) with alkylammonium ligands substituting into some surface Cs sites, consistent with the surface-selective 133 Cs NMR experiments. These results highlight the utility of high-resolution solid-state NMR spectroscopy for studying ligand binding and the surface structure of nanomaterials.

We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. It also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core-shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na 2 Se 2 (hcp) and Na 2 Se (fcc). A nanoscale fracture of terminally sodiated Na-Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na + diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their "free" counterparts.

Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO 3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO 3 completely converts PE ( M n = 8000-158,000 Da) or a single-use plastic bag ( M n = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H 2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight ( M n ) and the narrow polydispersity ( Đ ) of the final liquid product. Solid-state nuclear magnetic resonance of 13 C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO 3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons., Competing Interests: The authors declare the following competing financial interest(s): Two patent applications partially based on this work have been filed (US Patent Applications 62/796,482 and 62/892,347)., (Copyright © 2019 American Chemical Society.)

In spite of the widespread applications of amorphous silica-aluminas (ASAs) in many important industrial chemical processes, their high-resolution structures have remained largely elusive. Specifically, the lack of long-range ordering in ASA precludes the use of diffraction methods while NMR spectroscopy has been limited by low sensitivity. Here, we use conventional as well as DNP-enhanced 29 Si- 29 Si, 27 Al- 27 Al, and 29 Si- 27 Al solid-state NMR experiments to shed light on the ordering of atoms in ASAs prepared by flame-spray-pyrolysis. These experiments, in conjunction with a novel Monte Carlo-based approach to simulating RESPDOR dephasing curves, revealed that ASA materials obey Loewenstein's rule of aluminum avoidance. 3D 17 O{ 1 H} and 2D 17 O{ 1 H, 27 Al} experiments were developed to measure site-specific O-H and HO-Al distances, and show that the Brønsted acid sites originate predominantly from the pseudo-bridging silanol groups.

High-field magic angle spinning dynamic nuclear polarization (MAS DNP) is often used to enhance the sensitivity of solid-state nuclear magnetic resonance experiments by transferring spin polarization from electron spins to nuclear spins. Here, we demonstrate that γ-irradiation induces the formation of stable radicals in inorganic solids, such as fused quartz and borosilicate glasses, as well as organic solids, such as glucose, cellulose, and a urea/polyethylene polymer. The radicals were then used to polarize 29 Si or 1 H spins in the core of some of these materials. Significant MAS DNP enhancements (ε) of more than 400 and 30 were obtained for fused quartz and glucose, respectively. For other samples, negligible values of ε were obtained, likely due to low concentrations of radicals or the presence of abundant quadrupolar spins. These results demonstrate that ionizing radiation is a promising alternative method for generating stable radicals that are suitable for high-field MAS DNP experiments.

We investigated the utility of locally restricting the basis sets involved in low-order correlations in Liouville space (LCL) calculations of spin diffusion. Using well-known classical models of spin diffusion, we describe a rationale for selecting the optimal basis set for such calculations. We then show that the use of these locally restricted basis sets provides the same computational accuracy as the full LCL set while reducing the computational time by several orders of magnitude. Speeding up the calculations also enables us to use higher maximum spin orders and increase the computational accuracy. Furthermore, unlike exact and full LCL calculations, locally restricted LCL calculations scale linearly with the system size and should thus enable the ab initio study of spin diffusion in spin systems containing several thousand spins.

Single-site supported organometallic catalysts bring together the favorable aspects of homogeneous and heterogeneous catalysis while offering opportunities to investigate the impact of metal-support interactions on reactivity. We report a ( dm Phebox)Ir(III) ( dm Phebox = 2,6-bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl) complex chemisorbed on sulfated zirconia, the molecular precursor for which was previously applied to hydrocarbon functionalization. Spectroscopic methods such as diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS), dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) spectroscopy, and X-ray absorption spectroscopy (XAS) were used to characterize the supported species. Tetrabutylammonium acetate was found to remove the organometallic species from the surface, enabling solution-phase analytical techniques in conjunction with traditional surface methods. Cationic character was imparted to the iridium center by its grafting onto sulfated zirconia, imbuing high levels of activity in electrophilic C-H bond functionalization reactions such as the stoichiometric dehydrogenation of alkanes, with density functional theory (DFT) calculations showing a lower barrier for β-H elimination. Catalytic hydrogenation of olefins was also facilitated by the sulfated zirconia-supported ( dm Phebox)Ir(III) complex, while the homologous complex on silica was inactive under comparable conditions.

The sensitivity of solid-state NMR experiments that utilize 1 H zero-quantum heteronuclear dipolar recoupling, such as D-HMQC, is compromised by poor homonuclear decoupling. This leads to a rapid decay of recoupled magnetization and an inefficient recoupling of long-range dipolar interactions, especially for nuclides with low gyromagnetic ratios. We investigated the use, in symmetry-based 1 H heteronuclear recoupling sequences, of a basic R element that was principally designed for efficient homonuclear decoupling. By shortening the time required to suppress the effects of homonuclear dipolar interactions to the duration of a single inversion pulse, spin diffusion was effectively quenched and long-lived recoupled coherence lifetimes could be obtained. We show, both theoretically and experimentally, that these modified sequences can yield considerable sensitivity improvements over the current state-of-the-art methods and applied them to the indirect detection of 89 Y in a metal-organic framework., (Published by Elsevier Inc.)

The so-called t 1 noise, which arises due to random instabilities in the spectrometer hardware, remains the primary source of noise that limits the sensitivity of most 2D NMR experiments, particularly in the expanding group of solid-state NMR methods that utilize dipolar-recoupling. In this communication we revisit the relationship between the signal intensity and the t 1 noise produced. It is shown that since the latter scales linearly with the signal strength, the use of a conventional relaxation delay of 1.3T 1 may prove far from optimal. In cases where the fluctuations occur on a shorter timescale than the recycle delay, a considerably faster repetition rate should be used to maximize the time sensitivity in a 2D experiment than what is used to maximize the sensitivity in 1D. This is demonstrated with the acquisition of 1 H{ 13 C} Dipolar-mediated Heteronuclear Multiple-Quantum Correlation (D-HMQC) type spectra in which the sensitivity could be nearly doubled by choosing a very short relaxation delay corresponding to 0.2T 1 ., (Published by Elsevier Inc.)

Magic-angle-spinning (MAS) dynamic nuclear polarization (DNP) has recently emerged as a powerful technology enabling otherwise unrealistic solid-state NMR experiments. The simulation of DNP processes which might, for example, aid in refining the experimental conditions or the design of better performing polarizing agents, is, however, plagued with significant challenges, often limiting the system size to only 3 spins. Here, we present the first approach to fully ab initio large-scale simulations of MAS DNP enhancements. The Landau-Zener equation is used to treat all interactions concerning electron spins, and the low-order correlations in the Liouville space method is used to accurately treat the spin diffusion, as well as its MAS speed dependence. As the propagator cannot be stored, a Monte Carlo optimization method is used to determine the steady-state enhancement factors. This new software is employed to investigate the MAS speed dependence of the enhancement factors in large spin systems where spin diffusion is of importance, as well as to investigate the impacts of solvent and polarizing agent deuteration on the performance of MAS DNP.

The chemical and electronic interactions of organometallic species with metal oxide support materials are of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe 3 )IrMe 2 on sulfated alumina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organometallic precursors toward trityl cation ([Ph 3 C] + ), a Lewis acid known to effect formal hydride abstraction by one-electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration as well as the extent of dehydration under thermal activation conditions of SA and SZ supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron-deficient pyrosulfate species as the redox-active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organometallic complexes but also in the larger context of their application as catalysts for the transformation of light alkanes.

We utilize direct 17O DNP for the characterization of non-protonated oxygens in heterogeneous catalysts. The optimal sample preparation and population transfer approach for 17O direct DNP experiments performed on silica surfaces is determined and applied to the characterization of Zr- and Y-based mesoporous silica-supported single-site catalysts.

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO 2 support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV-vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H 2 and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO 2 , 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe 3 with Zn(II)-modified SiO 2 support is thermodynamically favorable (Δ G = -12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH 3 -TPD and DNP-enhanced 17 O{ 1 H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1 H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. We also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. Generally, any condition in which the g yy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. Our results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Lastly, the calculations showed that the electron T 1e value should be near 500 μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)