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Metal halide perovskites of the general formula ABX3-where A is a monovalent cation such as caesium, methylammonium or formamidinium; B is divalent lead, tin or germanium; and X is a halide anion-have shown great potential as light harvesters for thin-film photovoltaics1-5. Among a large number of compositions investigated, the cubic α-phase of formamidinium lead triiodide (FAPbI3) has emerged as the most promising semiconductor for highly efficient and stable perovskite solar cells6-9, and maximizing the performance of this material in such devices is of vital importance for the perovskite research community. Here we introduce an anion engineering concept that uses the pseudo-halide anion formate (HCOO-) to suppress anion-vacancy defects that are present at grain boundaries and at the surface of the perovskite films and to augment the crystallinity of the films. The resulting solar cell devices attain a power conversion efficiency of 25.6 per cent (certified 25.2 per cent), have long-term operational stability (450 hours) and show intense electroluminescence with external quantum efficiencies of more than 10 per cent. Our findings provide a direct route to eliminate the most abundant and deleterious lattice defects present in metal halide perovskites, providing a facile access to solution-processable films with improved optoelectronic performance.
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Triphenylphosphine (PPh3) is a ubiquitous ligand in organometallic chemistry that has been shown to give enhanced 31P NMR signals at high magnetic field via a scalar-dominated Overhauser effect dynamic nuclear polarization (OE DNP). However, PPh3 can only be polarized via DNP in the free form, while the coordinated form is DNP-inactive. Here, we demonstrate the possibility of enhancing the 31P NMR signals of coordinated PPh3 in metal complexes in solution at room temperature by combining Overhauser effect DNP and chemical exchange between the free and coordinated PPh3 forms. With this method, we successfully obtain 31P DNP enhancements of up to 2 orders of magnitude for the PPh3 ligands in Rh(I), Ru(II), Pd(II), and Pt(II) complexes, and we show that the DNP enhancements can be used to determine the activation energy of the ligand exchange reaction.
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Lanthanides are versatile modulators of optoelectronic properties owing to their narrow optical emission spectra across the visible and near-infrared range. Their use in metal halide perovskites (MHPs) has recently gained prominence, although their fate in these materials has not yet been established at the atomic level. We use cesium-133 solid-state NMR to establish the speciation of all nonradioactive lanthanide ions (La3+, Ce3+, Pr3+, Nd3+, Sm3+, Sm2+, Eu3+, Eu2+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+) in microcrystalline CsPbCl3. Our results show that all lanthanides incorporate into the perovskite structure of CsPbCl3 regardless of their oxidation state (+2, +3).
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The inherently low sensitivity of nuclear magnetic resonance (NMR) spectroscopy is the major limiting factor for its application to elucidate structure and dynamics in solids. In the solid state, nuclear spin hyperpolarization methods based on microwave-induced dynamic nuclear polarization (DNP) provide a versatile platform to enhance the bulk NMR signal of many different sample formulations, leading to significant sensitivity improvements. Here we show that 1H NMR hyperpolarization can also be generated in solids at high magnetic fields by optical irradiation of the sample. We achieved this by exploiting a donor-chromophore-acceptor molecule with an excited state electron-electron interaction similar to the nuclear Larmor frequency, enabling solid-state 1H photochemically induced DNP (photo-CIDNP) at high magnetic fields. Through hyperpolarization relay, we obtained bulk NMR signal enhancements εH by factors of â¼100 at both 9.4 and 21.1 T for the 1H signal of o-terphenyl in magic angle spinning (MAS) NMR experiments at 100 K. These findings open a pathway toward a general light-induced hyperpolarization approach for dye-sensitized high-field NMR in solids.
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1H-detected dynamic nuclear polarization (DNP)-enhanced fast magic angle spinning (MAS) NMR experiments provide unprecedented sensitivity to study the structure and dynamics in advanced materials and biomolecules. However, in relayed DNP experiments, DNP enhancements decrease with faster MAS rates, which is detrimental for sensitivity. The decrease is because 1H-1H spin diffusion rates are significantly reduced at fast MAS frequencies. To improve sensitivity at these fast MAS rates, here, we propose to combine fast polarization build-up by relay at slow MAS rate with high-resolution 1H NMR at fast MAS for acquisition. We perform experiments on l-histidine·HCl·H2O with MAS rates of up to 65 kHz using a 0.7 mm DNP probe at 18.8 T and 100 K. We obtain a 35% improvement in sensitivity in experiments where the sample is polarized at 20 kHz MAS and where the signal is acquired at 60 kHz MAS.
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We evaluate the overall sensitivity gains provided by a series of eighteen nitroxide biradicals for dynamic nuclear polarization (DNP) solid-state NMR at 9.4â T and 100â K, including eight new biradicals. We find that in the best performing group the factors contributing to the overall sensitivity gains, namely the DNP enhancement, the build-up time, and the contribution factor, often compete with each other leading to very similar overall sensitivity across a range of biradicals. NaphPol and HydroPol are found to provide the best overall sensitivity factors, in organic and aqueous solvents respectively. One of the new biradicals, AMUPolCbm, provides high sensitivity for all three solvent formulations measured here, and can be considered to be a "universal" polarizing agent.
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Bandgap-tuneable mixed-halide 3D perovskites are of interest for multi-junction solar cells, but suffer from photoinduced spatial halide segregation. Mixed-halide 2D perovskites are more resistant to halide segregation and are promising coatings for 3D perovskite solar cells. The properties of mixed-halide compositions depend on the local halide distribution, which is challenging to study at the level of single octahedra. In particular, it has been suggested that there is a preference for occupation of the distinct axial and equatorial halide sites in mixed-halide 2D perovskites. 207 Pb NMR can be used to probe the atomic-scale structure of lead-halide materials, but although the isotropic 207 Pb shift is sensitive to halide stoichiometry, it cannot distinguish configurational isomers. Here, we use 2D isotropic-anisotropic correlation 207 Pb NMR and relativistic DFT calculations to distinguish the [PbX6 ] configurations in mixed iodide-bromide 3D FAPb(Br1-x Ix )3 perovskites and 2D BA2 Pb(Br1-x Ix )4 perovskites based on formamidinium (FA+ ) and butylammonium (BA+ ), respectively. We find that iodide preferentially occupies the axial site in BA-based 2D perovskites, which may explain the suppressed halide mobility.
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Structure determination of molecular solids through NMR crystallography relies on the generation of a comprehensive set of candidate crystal structures and on the comparison of chemical shifts computed for those candidates with experimental values. Exploring the polymorph landscape of molecular solids requires extensive computational power, which leads to a significant bottleneck in the generation of the set of candidate crystals by crystal structure prediction (CSP) protocols. Here, we use a database of crystal structures with associated chemical shifts to construct three-dimensional interaction maps in molecular crystals directly derived from a molecular structure and its associated set of experimentally measured chemical shifts. We show how the maps obtained can be used to identify structural constraints for accelerating CSP protocols and to evaluate the likelihood of candidate crystal structures without requiring DFT-level chemical shift computations.
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The organic cations in hybrid organic-inorganic perovskites rotate rapidly inside the cuboctahedral cavities formed by the inorganic lattice, influencing optoelectronic properties. Here, we provide a complete quantitative picture of cation dynamics for formamidinium-based perovskites and mixed-cation compositions, which are the most widely used and promising absorber layers for perovskite solar cells today. We use 2H and 14N quadrupolar solid-state NMR relaxometry under magic-angle spinning to determine the activation energy (Ea) and correlation time (τc) at room temperature for rotation about each principal axis of a series of organic cations. Specifically, we investigate methylammonium (MA+), formamidinium (FA+), and guanidinium (GUA+) cations in current state-of-the-art single- and multi-cation perovskite compositions. We find that MA+, FA+, and GUA+ all have at least one component of rotation that occurs on the picosecond timescale at room temperature, with MA+ and GUA+ also exhibiting faster and slower components, respectively. The cation dynamics depend on the symmetry of the inorganic lattice but are found to be insensitive to the degree of cation substitution. In particular, the FA+ rotation is invariant across all compositions studied here, when sufficiently above the phase transition temperature. We further identify an unusual relaxation mechanism for the 2H of MA+ in mechanosynthesized FAxMA1-xPbI3, which was found to result from physical diffusion to paramagnetic defects. This precise picture of cation dynamics will enable better understanding of the relationship between the organic cations and the optoelectronic properties of perovskites, guiding the design principles for more efficient perovskite solar cells in the future.
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The physical properties of many modern multi-component materials are determined by their internal microstructure. Tools capable of characterizing complex nanoscale architectures in composite materials are, therefore, essential to design materials with targeted properties. Depending on the morphology and the composition, structures may be measured by laser diffraction, scattering methods, or by electron microscopy. However, it can be difficult to obtain contrast in materials where all the components are organic, which is typically the case for formulated pharmaceuticals, or multi-domain polymers. In nuclear magnetic resonance (NMR) spectroscopy, chemical shifts allow a clear distinction between organic components and can in principle provide the required chemical contrast. Here, we introduce a method to obtain radial images of the internal structure of multi-component particles from NMR measurements of the relay of nuclear hyperpolarization obtained from dynamic nuclear polarization. The method is demonstrated on two samples of hybrid core-shell particles composed of a core of polystyrene with a shell of mesostructured silica filled with the templating agent CTAB and is shown to yield accurate images of the core-shell structures with a nanometer resolution.
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Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor-acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for 13C and 15N nuclei. However, the low gyromagnetic ratio and natural abundance of these nuclei trap the local hyperpolarization in the vicinity of the chromophore and limit the utility for bulk hyperpolarization. Here, we report the first example of optically enhanced solid-state 1H NMR spectroscopy in the high-field regime. This is achieved via photo-CIDNP of a donor-chromophore-acceptor molecule in a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusion among the abundant strongly coupled 1H nuclei relays polarization through the whole sample, yielding a 16-fold bulk 1H signal enhancement under continuous laser irradiation at 450 nm. These findings enable a new strategy for hyperpolarized NMR beyond the current limits of conventional microwave-driven DNP.
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Protein-based drugs are becoming increasingly important, but there are challenges associated with their formulation (for example, formulating stable inhalable aerosols while maintaining the proper long-term stability of the protein). Determining the morphology of multicomponent, protein-based drug formulations is particularly challenging. Here, we use dynamic nuclear polarization (DNP) solid-state NMR spectroscopy to determine the hierarchy of components within spray-dried particles containing protein, trehalose, leucine, and trileucine. DNP NMR was applied to these formulations to assess the localization of the components within the particles. We found a consistent scheme, where trehalose and the protein are co-located within the same phase in the core of the particles and leucine and trileucine are distributed in separate phases at the surface of the particles. The description of the hierarchy of the organic components determined by DNP NMR enables the rationalization of the performance of the formulation.
Assuntos
Excipientes , Trealose , Leucina/química , Trealose/química , Excipientes/química , Aerossóis/química , Espectroscopia de Ressonância Magnética , Pós/química , Administração por Inalação , Tamanho da PartículaRESUMO
Magic angle spinning (MAS) in 1H NMR has allowed progress from featureless spectra in static samples to linewidths of a few hundreds of Hertz for powdered solids at the fastest spinning rates available today (100-150 kHz). While this is a remarkable improvement, this level of resolution is still limiting to the widespread use of 1H NMR for complex systems. This review will discuss two recent alternative strategies that have significantly improved 1H resolution, when combined with fast MAS. The first is based on anti-z-COSY, a 2D experiment originally used for J decoupling in liquids, which removes residual broadening due to splittings caused by imperfect coherent averaging of MAS. The second strategy is to obtain pure isotropic proton (PIP) spectra in solids, by parametrically mapping any residual broadening due to imperfect averaging into a second dimension of a multidimensional correlation spectrum.
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The resolution of proton solid-state NMR spectra is usually limited by broadening arising from dipolar interactions between spins. Magic-angle spinning alleviates this broadening by inducing coherent averaging. However, even the highest spinning rates experimentally accessible today are not able to completely remove dipolar interactions. Here, we introduce a deep learning approach to determine pure isotropic proton spectra from a two-dimensional set of magic-angle spinning spectra acquired at different spinning rates. Applying the model to 8 organic solids yields high-resolution 1 H solid-state NMR spectra with isotropic linewidths in the 50-400â Hz range.
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One key bottleneck of solid-state NMR spectroscopy is that 1 H NMR spectra of organic solids are often very broad due to the presence of a strong network of dipolar couplings. We have recently suggested a new approach to tackle this problem. More specifically, we parametrically mapped errors leading to residual dipolar broadening into a second dimension and removed them in a correlation experiment. In this way pure isotropic proton (PIP) spectra were obtained that contain only isotropic shifts and provide the highest 1 H NMR resolution available today in rigid solids. Here, using a deep-learning method, we extend the PIP approach to a second dimension, and for samples of L-tyrosine hydrochloride and ampicillin we obtain high resolution 1 H-1 H double-quantum/single-quantum dipolar correlation and spin-diffusion spectra with significantly higher resolution than the corresponding spectra at 100â kHz MAS, allowing the identification of previously overlapped isotropic correlation peaks.
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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 9.4â 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.
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Determination of the three-dimensional atomic-level structure of powdered solids is one of the key goals in current chemistry. Solid-state NMR chemical shifts can be used to solve this problem, but they are limited by the high computational cost associated with crystal structure prediction methods and density functional theory chemical shift calculations. Here, we successfully determine the crystal structures of ampicillin, piroxicam, cocaine, and two polymorphs of the drug molecule AZD8329 using on-the-fly generated machine-learned isotropic chemical shifts to directly guide a Monte Carlo-based structure determination process starting from a random gas-phase conformation.
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Imageamento por Ressonância Magnética , Espectroscopia de Ressonância Magnética , Método de Monte CarloRESUMO
Surface and bulk molecular modulators are the key to improving the efficiency and stability of hybrid perovskite solar cells. However, due to their low concentration, heterogeneous environments, and low sample mass, it remains challenging to characterize their structure and dynamics at the atomic level, as required to establish structure-activity relationships. Nuclear magnetic resonance (NMR) spectroscopy has revealed a wealth of information on the atomic-level structure of hybrid perovskites, but the inherent insensitivity of NMR severely limits its utility to characterize thin-film samples. Dynamic nuclear polarization (DNP) can enhance NMR sensitivity by orders of magnitude, but DNP methods for perovskite materials have so far been limited. Here, we determined the factors that limit the efficiency of DNP NMR for perovskite samples by systematically studying layered hybrid perovskite analogues. We find that the fast-relaxing dynamic cation is the major impediment to higher DNP efficiency, while microwave absorption and particle morphology play a secondary role. We then show that the former can be mitigated by deuteration, enabling 1H DNP enhancement factors of up to 100, which can be harnessed to enhance signals from dopants or additives present in very low concentrations. Specifically, using this new DNP methodology at a high magnetic field and with small sample volumes, we have recorded the NMR spectrum of the 20 nm (6 µg) passivating layer on a single perovskite thin film, revealing a two-dimensional (2D) layered perovskite structure at the surface that resembles the n = 1 homologue but which has greater disorder than in bulk layered perovskites.
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It has recently been demonstrated that the addition of zinc can enhance the mechanical strength of tricalcium silicates (C3S) upon hydration, but the structure of the main hydration product of cement, calcium silicate hydrate (C-S-H), in zinc-modified formulations remains unresolved. Here, we combine 29Si DNP-enhanced solid-state nuclear magnetic resonance (NMR), density functional theory (DFT)-based chemical shift computations, and molecular dynamics (MD) modeling to determine the atomic-level structure of zinc-modified C-S-H. The structure contains two main new silicon species (Q(1,Zn) and Q(2p,Zn)) where zinc substitutes Q(1) silicon species in dimers and bridging Q(2b) silicon sites, respectively. Structures determined as a function of zinc content show that zinc promotes an increase in the dreierketten mean chain lengths.
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Silício , Zinco , Zinco/química , Compostos de Cálcio/química , Silicatos/químicaRESUMO
The determination of intracellular drug concentrations can provide a better understanding of the drug function and efficacy. Ideally, this should be performed nondestructively, with no modification of either the drug or the target, and with the capability to detect low amounts of the molecule of interest, in many cases in the µM to nM range (pmol to fmol per million cells). Unfortunately, it is currently challenging to have an experimental technique that provides direct quantitative measurements of intracellular drug concentrations that simultaneously satisfies these requirements. Here, we show that magic-angle spinning dynamic nuclear polarization (MAS DNP) can be used to fulfill these requirements. We apply a quantitative 15N MAS DNP approach in combination with 15N labeling to quantify the intracellular amount of the drug [15N]CHIR-98014, an activator of the Wingless and Int-1 signaling pathway, determining intracellular drug amounts in the range of tens to hundreds of picomoles per million cells. This is, to our knowledge, the first time that MAS DNP has been used to successfully estimate intracellular drug amounts.