Observation of H-H J-couplings in fast magic-angle-spinning solid-state NMR spectroscopy.

While H-H J-couplings are the cornerstone of all spectral assignment methods in solution-state NMR, they are yet to be observed in solids. Here we observe H-H J-couplings in plastic crystals of (1S)-(-)-camphor in solid-state NMR at magic angle spinning (MAS) rates of 100 kHz and above. This is enabled in this special case because the intrinsic coherence lifetimes at fast MAS rates become longer than the inverse of the H-H J couplings.

Solid Effect Dynamic Nuclear Polarization Enhancement of >500 at 9.4 T.

Efficient polarizing agents for dynamic nuclear polarization (DNP) enhanced magic angle spinning (MAS) NMR spectroscopy are of high current interest due to the potential to significantly boost NMR sensitivity. While most efforts have centered on cross-effect (CE) or Overhauser effect (OE) mechanisms, yielding enhancement factors up to ∼300 at 9.4 T, radicals yielding solid effect (SE) DNP have seen less development.

An Efficient and Stable Polarizing Agent for In-Cell Magic-Angle Spinning Dynamic Nuclear Polarization NMR Spectroscopy.

Nuclear Magnetic Resonance (NMR) spectroscopy would be a method of choice to follow biochemical events in cells because it can analyze molecules in complex environments. However, the intrinsically low sensitivity of NMR makes in-cell measurements challenging. Dynamic Nuclear Polarization (DNP) has emerged as a method to circumvent this limitation, but most polarizing agents developed for DNP are unstable in reducing cellular environments.

Mechanism of Solid-State H Photochemically Induced Dynamic Nuclear Polarization in a Synthetic Donor-Chromophore-Acceptor at 0.3 T.

H photochemically induced dynamic nuclear polarization (photo-CIDNP) has recently emerged as a tool to enhance bulk H nuclear magnetic resonance (NMR) signals in solids at magnetic fields ranging from 0.3 to 21.1 T, using synthetic donor-chromophore-acceptor (D-C-A) molecules as optically active polarizing agents (PAs).

Formamidinium Incorporates into Rb-based Non-Perovskite Phases in Solar Cell Formulations.

Organic-inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non-perovskite phase complicates the application of FAPbI in solar cells. To remedy this, alkali metal cations, most often Cs, Rb or K, are included during perovskite synthesis to stabilize the photoactive phase.

Light-Induced Metallic and Paramagnetic Defects in Halide Perovskites from Magnetic Resonance.

Halide perovskites are promising next-generation solar cell materials, but their commercialization is hampered by their propensity to degrade under operating conditions, particularly under heat, humidity, and light. Identifying degradation products and linking them to the degradation mechanism at the atomic scale is necessary to design more stable perovskite materials. Here we use magnetic resonance methods to identify and characterize the formation of both metallic lead clusters and Pb defects upon light-induced degradation of methylammonium lead halide perovskite using nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) measurements.

Spiers Memorial Lecture: NMR crystallography.

Chemical function is directly related to the spatial arrangement of atoms. Consequently, the determination of atomic-level three-dimensional structures has transformed molecular and materials science over the past 60 years. In this context, solid-state NMR has emerged to become the method of choice for atomic-level characterization of complex materials in powder form.

Efficient DNP at high fields and fast MAS with antenna-sensitized dinitroxides.

Dynamic Nuclear Polarization (DNP) can significantly enhance the sensitivity of solid-state NMR. In DNP, microwave irradiation induces polarization transfer from unpaired electron spins to H nuclear spins hyperfine couplings and spin-diffusion. The structure of the polarizing agents that host the electron spins is key for DNP efficiency.

Crystal structure validation of verinurad proton-detected ultra-fast MAS NMR and machine learning.

The recent development of ultra-fast magic-angle spinning (MAS) (>100 kHz) provides new opportunities for structural characterization in solids. Here, we use NMR crystallography to validate the structure of verinurad, a microcrystalline active pharmaceutical ingredient. To do this, we take advantage of H resolution improvement at ultra-fast MAS and use solely H-detected experiments and machine learning methods to assign all the experimental proton and carbon chemical shifts.

Atomic-level structure of the amorphous drug atuliflapon NMR crystallography.

We determine the complete atomic-level structure of the amorphous form of the drug atuliflapon, a 5-lipooxygenase activating protein (FLAP) inhibitor, chemical-shift-driven NMR crystallography. The ensemble of preferred structures allows us to identify a number of specific conformations and interactions that stabilize the amorphous structure. These include preferred hydrogen-bonding motifs with water and with other drug molecules, as well as conformations of the cyclohexane and pyrazole rings that stabilize structure by indirectly allowing for optimization of hydrogen bonding.

Stabilization of highly efficient perovskite solar cells with a tailored supramolecular interface.

The presence of defects at the interface between the perovskite film and the carrier transport layer poses significant challenges to the performance and stability of perovskite solar cells (PSCs). Addressing this issue, we introduce a dual host-guest (DHG) complexation strategy to modulate both the bulk and interfacial properties of FAPbI-rich PSCs. Through NMR spectroscopy, a synergistic effect of the dual treatment is observed.

Hydrogen Diffusion in Hybrid Perovskites from Exchange NMR.

Ion migration is an important phenomenon affecting the performance of hybrid perovskite solar cells. It is particularly challenging, however, to disentangle the contribution of H diffusion from that of other ions, and the atomic-scale mechanism remains unclear. Here, we use H exchange NMR to prove that H ions exchange between MA cations on the time scale of seconds for both MAPbI and FAMAPbI perovskites.

Maximizing Relayed H Hyperpolarization Transfer by Slow-Fast MAS NMR Spectroscopy.

H-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 H-H spin diffusion rates are significantly reduced at fast MAS frequencies.

Observation of Transient Prenucleation Species of Calcium Carbonate by DNP-Enhanced NMR.

Knowledge of the mechanism by which polymorphic inorganic species, such as carbonates, are formed is crucial to understand and guide the selective crystallization of end products. Recently it has been shown that a key step in the crystallization of calcium carbonate is the formation of intermediate species known as prenucleation clusters. However, the observation of these prenucleation clusters in solution is exceedingly challenging because of their short lifetime and low concentrations.

Light-Induced H NMR Hyperpolarization in Solids at 9.4 and 21.1 T.

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 H NMR hyperpolarization can also be generated in solids at high magnetic fields by optical irradiation of the sample.

Magic Angle Spinning Solid-State C Photochemically Induced Dynamic Nuclear Polarization by a Synthetic Donor-Chromophore-Acceptor System at 9.4 T.

Solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) is a nuclear magnetic resonance spectroscopy technique in which nuclear spin hyperpolarization is generated upon optical irradiation of an appropriate donor-acceptor system. Until now, solid-state photo-CIDNP at high magnetic fields has been observed only in photosynthetic reaction centers and flavoproteins. In the present work, we show that the effect is not limited to such biomolecular samples, and solid-state C photo-CIDNP can be observed at 9.

Probing Homogeneous Catalysts and Precatalysts in Solution by Exchange-Mediated Overhauser Dynamic Nuclear Polarization NMR.

Triphenylphosphine (PPh) is a ubiquitous ligand in organometallic chemistry that has been shown to give enhanced P NMR signals at high magnetic field via a scalar-dominated Overhauser effect dynamic nuclear polarization (OE DNP). However, PPh 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 P NMR signals of coordinated PPh in metal complexes in solution at room temperature by combining Overhauser effect DNP and chemical exchange between the free and coordinated PPh forms.

Speciation of Lanthanide Metal Ion Dopants in Microcrystalline All-Inorganic Halide Perovskite CsPbCl.

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 (La, Ce, Pr, Nd, Sm, Sm, Eu, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) in microcrystalline CsPbCl.

Optimal sensitivity for H detected relayed DNP of organic solids at fast MAS.

Dynamic nuclear polarization (DNP) combined with high magnetic fields and fast magic angle spinning (MAS) has opened up a new avenue for the application of exceptionally sensitive H NMR detection schemes to study protonated solids. Recently, it has been shown that DNP experiments at fast MAS rates lead to slower spin diffusion and hence reduced DNP enhancements for impregnated materials. However, DNP enhancements alone do not determine the overall sensitivity of a NMR experiment.

Axial-Equatorial Halide Ordering in Layered Hybrid Perovskites from Isotropic-Anisotropic Pb NMR.

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.

Rational Design of Dinitroxide Polarizing Agents for Dynamic Nuclear Polarization to Enhance Overall NMR Sensitivity.

We evaluate the overall sensitivity gains provided by a series of eighteen nitroxide biradicals for dynamic nuclear polarization (DNP) solid-state NMR at 9.4 T and 100 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.

Improvements in Resolution of ¹H NMR of solids.

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.