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Zeolite-formation mechanisms have long been the subject of intensive study, with most work concentrating on hydrothermal mechanisms. However, non-traditional zeolite syntheses that do not rely on hydrothermal crystallisation have provided a number of new routes to interesting and unexpected new materials, but their formation mechanisms remain poorly understood. Here, we show how simultaneous in situ liquid- and solid-state 29 Si NMR spectroscopy can reveal the mechanism of the formation of a zeolite from a layered silicate precursor. The study provides evidence for the species that are intercalated into the layered material and establishes those that are involved in building the inter-layer, zeolitic connections as a function of time during the zeolite formation process., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

This Faraday Discussion explored the field of NMR crystallography, and considered recent developments in experimental and theoretical approaches, new advances in machine learning and in the generation and handling of large amounts of data. Applications to a wide range of disordered, amorphous and dynamic systems demonstrated the range and quality of information available from this approach and the challenges that are faced in exploiting automation and developing best practice. In these closing remarks I will reflect on the discussions on the current state of the art, questions about what we want from these studies, how accurate we need results to be, how we best generate models for complex materials and what machine learning approaches can offer. These remarks close with thoughts about the future direction of the field, who will be carrying out this type of research, how they might be doing it and what their focus will be, along with likely possible challenges and opportunities.

Zeolites contain extraframework cations that are exchangeable under favorable aqueous conditions; this is the fundamental feature for their application in water purification and necessary to produce cation forms for other applications such as catalysis. Optimization of the process is common, but there is little fundamental understanding based on real-time experiments of the mechanism of exchange for most zeolites. The sodium and potassium forms of zeolite chabazite selectively uptake Cs + by ion exchange, leading to its application in removing radioactive 137 Cs + from industrial nuclear waste streams, as well as from contaminated environments in the aftermath of the Fukushima and Three Mile Island accidents. In this study, in situ synchrotron powder X-ray diffraction patterns have been collected on chabazite as it undergoes Cs-ion exchange. Applying Rietveld refinement to these patterns has revealed the time-resolved structural changes that occur in the zeolite as exchange progresses, charting the changes in the spatial distribution of the extraframework cations and water molecules in the structure during the reaction. Ultimately, a detailed mechanistic understanding of how this dynamic ion-exchange reaction occurs has been obtained., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

We use a combination of one- and two-dimensional solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations to obtain a full assignment of the 1 H and 13 C signals for solid (+)-usnic acid, which contains two molecules in the asymmetric unit. By combining through-space 1 H- 1 H correlation data with computation it is possible to assign signals not just to the same molecules (relative assignment) but to assign the signals to specific crystallographic molecules (absolute assignment). Variable-temperature measurements reveal that there is some variation in many of the 13 C chemical shifts with temperature, likely arising from varying populations of different tautomeric forms of the molecule. The NMR spectrum of crystalline (+)-usnic acid is then compared with that of ground Usnea dasopoga lichen (the source material of the usnic acid). The abundance of usnic acid is so great in the lichen that this natural product can be observed directly in the NMR spectrum without further purification. This natural sample of usnic acid appears to have the same crystalline form as that in the pure commercial sample.

The preparation of stable large pore aluminophosphate (AlPO) zeotypes offers materials for applications in adsorption and catalysis. Here we report the synthesis of the pure AlPO with the SAO topology type (AlPO STA-1) using N , N '-diethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidine (DEBOP) as the organic structure directing agent in the presence of fluoride. The AlPO STA-1 can be rendered microporous (pore volume 0.36 cm 3 g -1 ) via calcination and the calcined form remains stable in the presence of moisture. The structure of the dehydrated form has been established by Rietveld refinement (tetragonal P 4̄ n 2, a = 13.74317(10) Å, c = 21.8131(5) Å, V = 4119.94(16) Å 3 ). Multinuclear 27 Al and 31 P MAS NMR, together with 2D COSY and CASTEP NMR calculations, enables resolution and assignment of the signals from all crystallographically distinct Al and P framework sites. Structural elucidation of the as-prepared aluminophosphate-fluoride is more challenging, because of the presence of partially protonated OSDA molecules in the 3D-connected channel system and in particular because the fluoride ions coordinate with positional disorder to some of the Al atoms to give 5-fold as well as tetrahedrally-coordinated framework Al species. These are postulated to occupy Al-F-Al bridging sites, where they are responsible for distortion of the framework [ P 4̄ n 2, a = 13.3148(9) Å, c = 22.0655(20) Å, V = 3911.9(7) Å 3 ]. Calcination and removal of fluoride ions and OSDAs allows the framework to expand to its relaxed configuration. The SAO topology type aluminophosphate can also be synthesised with small amounts of Si and Ge in the framework, and these SAPO and GeAPO STA-1 materials are also stable to template removal. IR spectroscopy with CO as a probe at 123 K indicates all have weak-to-mild acidity, increasing in the order AlPO < GeAPO < SAPO. These STA-1 materials have been investigated for their activity in the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam at 598 K: while all are active, the AlPO form is favoured due to its high selectivity and slow deactivation, both of which are a consequence of its very weak acid strength, which is nevertheless sufficient to catalyse the reaction., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Sodium-ion batteries are emerging as a sustainable solution to tackle the growing global energy demands. In this context, organic electrode materials complement such technologies as they are composed of earth-abundant elements. As organic anodes, sodium carboxylates exhibit promising applicability in a wide range of molecules. To harness the advantages of individual systems and to minimise their limitations, in this work, an approach to form binary mixtures of sodium carboxylates using one-pot, microwave-assisted synthesis is presented. The target mixtures were synthesised in 30 min with disodium naphthalene-2,6-dicarboxylate (Na-NDC) as a common constituent in all. Both components in all mixtures were shown to participate in the charge storage and had a considerable effect on the performance characteristics, such as specific capacity and working voltage, in half and full cell formats. This approach opens a new avenue for enabling organic materials to be considered as more competitive candidates in sodium-ion batteries and promote their use in other material classes to overcome their limitations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report the first synthesis of the mixed-metal chabazite-type Al x Ga 1- x PO 4 -34(mim) solid solution, containing 1-methylimidazolium, mim, as structure directing agent (SDA), from the parent mixed-metal oxide solid solution, γ-(Al x Ga 1- x ) 2 O 3 . This hitherto unreported family of materials exhibits complex disorder, arising from the possible distributions of cations over available sites, the orientation of the SDA and the presence of variable amounts of water, which provides a prototype for understanding structural subtleties in nanoporous materials. In the as-made forms of the phosphate frameworks, there are three crystallographically distinct metal sites: two tetrahedral MO 4 and one octahedral MO 4 F 2 (M = Al, Ga). A combination of solid-state NMR spectroscopy and periodic DFT calculations reveals that the octahedral site is preferentially occupied by Al and the tetrahedral sites by Ga, leading to a non-random distribution of cations within the framework. Upon calcination to the Al x Ga 1- x PO 4 -34 framework, all metal sites are tetrahedral and crystallographically equivalent in the average R 3̄ symmetry. The cation distribution was explored by 31 P solid-state NMR spectroscopy, and it is shown that the non-random distribution demonstrated to exist in the as-made materials would be expected to give remarkably similar patterns of peak intensities to a random distribution owing to the change in average symmetry in the calcined materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO 2 ) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal-organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO 2 , bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO 2 to the open metal sites in this MOF (called chemisorption, where the adsorbent-adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent-adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO 2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO 2 of these sites when water is present. Further features of this site have been confirmed by variable SO 2 pressure scXRD studies, DFT calculations, and IR studies.

We present DFT predictions (CAM-B3LYP/II level) for the paramagnetic Nuclear Magnetic Resonance (pNMR) spectra of small molecular models based on the Cu(II)-paddlewheel dimer motif that is present in metal-organic frameworks (MOFs, notably the HKUST and STAM families). We explore potential point defects with spin-1/2 discovered through electron paramagnetic resonance (EPR) experiments. We consider defects through substitution of one Cu(II) centre in the dimer with protons, or through one-electron reduction, affording a mixed-valence dimer. While most of the defects have predicted pNMR shifts at room temperature in the range of those for the non-defective MOFs, their detection and assignment should be possible based on their distinct temperature dependence.

The assembly-disassembly-organization-reassembly (ADOR) process for the transformation of zeolite UTL using water has been studied by using 29 Si and 17 O solid-state NMR spectroscopy. The results show that the intermediate materials that are formed during the reaction are extremely dynamic and that the process involves both irreversible changes in structure that define the overall pathway and reversible lability of the Si-O-Si linkages that have no effect on the overall structure. The combination of processes occurring during the ADOR reaction means that the mechanism is considerably more complex than initially proposed., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Compositionally complex metal-organic frameworks (MOFs) have properties that depend on local structure that is often difficult to characterise. In this paper a density functional theory (DFT) computational study of mixed-metal (Al,Sc)-MIL-53, a flexible MOF with several different forms, was used to calculate the relative energetics of these forms and to predict NMR parameters that can be used to evaluate whether solid-state NMR spectroscopy can be used to differentiate, identify and characterise the forms adopted by mixed-metal MOFs of different composition. The NMR parameters can also be correlated with structural features in the different forms, giving fundamental insight into the nature and origin of the interactions that affect nuclear spins. Given the complexity of advanced NMR experiments required, and the potential need for expensive and difficult isotopic enrichment, the computational work is invaluable in predicting which experiments and approaches are likely to give the most information on the disorder, local structure and pore forms of these mixed-metal MOFs.

Cocoa pod husks (CPHs) represent an underutilized component of the chocolate manufacturing process. While industry's current focus is understandably on the cocoa beans, the husks make up around 75 wt % of the fruit. Previous studies have been dominated by the carbohydrate polymers present in CPHs, but this work highlights the presence of the biopolymer lignin in this biomass. An optimized organosolv lignin isolation protocol was developed, delivering significant practical improvements. This new protocol may also prove to be useful for agricultural waste-derived biomasses in general. NMR analysis of the high quality lignin led to an improved structural understanding, with evidence provided to support deacetylation of the lignin occurring during the optimized pretreatment. Chemical transformation, using a tosylation, azidation, copper-catalyzed click protocol, delivered a modified lignin oligomer with an organophosphorus motif attached. Thermogravimetric analysis was used to demonstrate the oligomer's potential as a flame-retardant. Preliminary analysis of the other product streams isolated from the CPHs was also carried out., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

A mixed-metal metal-organic framework, (Al,Ga)-MIL-53, synthesised by post-synthetic ion exchange has been investigated using solid-state nuclear magnetic resonance (NMR) spectroscopy, microscopy and energy dispersive X-ray (EDX) spectroscopy. 17 O enrichment during the ion-exchange process enables site specific information on the metal distribution to be obtained. Within this work two ion-exchange processes have been explored. In the first approach (exchange of metals in the framework with dissolved metal salts), 17 O NMR spectroscopy reveals the formation of crystallites with a core-shell structure, where the cation exchange takes place on the surface of these materials forming a shell with a roughly equal ratio of Al 3+ and Ga 3+ . For the second approach (exchange of metals between two frameworks), no core-shell structure is observed, and instead crystallites containing a majority of Al 3+ are obtained with lower levels of Ga 3+ . Noticeably, these particles show little variation in the metal cation distribution between crystallites, a result not previously observed for bulk (Al,Ga)-MIL-53 materials. In all cases where ion exchange has taken place NMR spectroscopy reveals a slight preference for clustering of like cations.

Postsynthetic modification of metal-organic frameworks (MOFs) has proven to be a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the μ 2 -OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for μ 2 -OCH 3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity - in this case chemisorption of methanol - has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

FeAPO-34 with a chabazite (CHA) topology structure was successfully synthesized under ionothermal conditions using 1-ethyl-3-methylimidazoliumchloride (EMIMCl) ionic liquid in the presence of ethylenediamine (EDA). The material was characterized using powder X-ray diffraction (XRD), thermogravimetric analysis (TGA), elemental analyses, and solid-state NMR spectroscopy. Incorporation of iron within the covalent framework of the material was confirmed by the presence of broad signals between 1000 and 14,000 ppm in the 31 P NMR spectrum, corresponding to the P(O Fe ) x (OAl) 4- x species.

An efficient protocol for the calculation of 13 C pNMR shifts in metal-organic frameworks based on Cu(ii) paddlewheel dimers is proposed, which involves simplified structural models, optimised using GFN2-xTB for the high-spin state, and CAM-B3LYP-computed NMR and EPR parameters. Models for hydrated and activated HKUST-1 and hydrated STAM MOFs with one, two and three Cu dimers have been used. The electronic ground states are low-spin and diamagnetic, with pNMR shifts arising from thermal population of intermediate- and high-spin excited states. Treating individual spin configurations in a broken symmetry (BS) approach, and selecting two or more of these to describe individual excited states, the magnetic shieldings of these paramagnetic states are evaluated using the approach by Hrobárik and Kaupp. The total shielding is then evaluated from a Boltzmann distribution between the energy levels of the chosen configurations. The computed pNMR shifts are very sensitive to temperature and, therefore, to the relative energies of the BS spin states. In order to reproduce the temperature dependence of the pNMR shifts seen in experiment, some scaling of the calculated energy gaps is required. A single scaling factor was applied to all levels in any one system, by fitting to experimental results at several temperatures simultaneously. The resulting scaling factor decreases with an increasing number of dimer units in the model ( e.g. , from ∼1.7 for mono-dimer models to 1.2 for tri-dimer models). The approach of this scaling factor towards unity indicates that models with three dimers are approaching a size where they can be considered as reasonable models for the 13 C shifts of infinite MOFs. The observed unusual temperature dependencies in the latter are indicated to arise both from the "normal" temperature dependence of the pNMR shifts of the paramagnetic states and the populations of these states in the thermal equilibrium., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Characterising the local structures (e.g., the cation distribution) of mixed-metal ceramics by NMR spectroscopy is often challenging owing to the unfavourable properties (low γ, large quadrupole moment and/or low abundance) of many metal nuclei. 17 O is an attractive option owing to the prevalence of oxygen within ceramics. The moderate γ and small quadrupole moment of 17 O mean that the greatest barrier to accessing the information available from this nucleus is isotopic enrichment. We explore the challenges of ensuring uniform isotopic enrichment with 17 O 2 (g) for the pyrochlore solid solutions, Y 2 Sn x Ti 2-x O 7 , La 2 Sn x Zr 2-x O 7 and La 2 Sn x Hf 2-x O 7 , demonstrating that high enrichment temperatures (900 °C for 12 hr) are required. In addition, for sites with very high symmetry (such as the tetrahedral OY4 and OLa4 sites with C Q  ≈ 0 present here), we demonstrate that quantitative 17 O NMR spectra require correction for the differing contributions from the centreband of the satellite transitions, which can be as high as a factor of ~3.89. It is common to use first-principles calculations to aid in interpreting NMR spectra of disordered solids. Here, we use an ensemble modelling approach to ensure that all possible cation arrangements are modelled in the minimum possible number of calculations. By combining uniform isotopic enrichment, quantitative NMR spectroscopy and a comprehensive computational approach, we are able to show that the cation distribution in Y 2 Sn x Ti 2-x O 7 is essentially random, whereas in La 2 Sn x Zr 2-x O 7 and La 2 Sn x Hf 2-x O 7 , OLa2SnZr and OLa2SnHf sites are slightly energetically disfavoured, leading to a weak preference for clustering of like cations., (© 2021 The Authors. Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.)

Microporous materials, containing pores and channels of similar dimensions to small molecules have a range of applications in catalysis, gas storage and separation and in drug delivery. Their complex structure, often containing different types and levels of positional, compositional and temporal disorder, makes structural characterisation challenging, with information on both long-range order and the local environment required to understand the structure-property relationships and improve the future design of functional materials. In principle, 17 O NMR spectroscopy should offer an ideal tool, with oxygen atoms lining the pores of many zeolites and phosphate frameworks, playing a vital role in host-guest chemistry and reactivity, and linking the organic and inorganic components of metal-organic frameworks (MOFs). However, routine study is challenging, primarily as a result of the low natural abundance of this isotope (0.037%), exacerbated by the presence of the quadrupolar interaction that broadens the spectral lines and hinders the extraction of information. In this Perspective, we will highlight the current state-of-the-art for 17 O NMR of microporous materials, focusing in particular on cost-effective and atom-efficient approaches to enrichment, the use of enrichment to explore chemical reactivity, the challenge of spectral interpretation and the approaches used to help this and the information that can be obtained from NMR spectra. Finally, we will turn to the remaining challenges, including further improving sensitivity, the high-throughput generation of multiple structural models for computational study and the possibility of in situ and in operando measurements, and give a personal perspective on how these required improvements can be used to help solve important problems in microporous materials chemistry., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Control over the spatial distribution of components in metal-organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal-organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core-shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core-shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Solid-state nuclear magnetic resonance (NMR) spectroscopy is an atomic-level method used to determine the chemical structure, three-dimensional structure, and dynamics of solids and semi-solids. This Primer summarizes the basic principles of NMR as applied to the wide range of solid systems. The fundamental nuclear spin interactions and the effects of magnetic fields and radiofrequency pulses on nuclear spins are the same as in liquid-state NMR. However, because of the anisotropy of the interactions in the solid state, the majority of high-resolution solid-state NMR spectra is measured under magic-angle spinning (MAS), which has profound effects on the types of radiofrequency pulse sequences required to extract structural and dynamical information. We describe the most common MAS NMR experiments and data analysis approaches for investigating biological macromolecules, organic materials, and inorganic solids. Continuing development of sensitivity-enhancement approaches, including 1 H-detected fast MAS experiments, dynamic nuclear polarization, and experiments tailored to ultrahigh magnetic fields, is described. We highlight recent applications of solid-state NMR to biological and materials chemistry. The Primer ends with a discussion of current limitations of NMR to study solids, and points to future avenues of development to further enhance the capabilities of this sophisticated spectroscopy for new applications., Competing Interests: Competing Interests There are no competing interests for all authors.

The synthesis of chiral metal-organic frameworks (MOFs) is highly relevant for asymmetric heterogenous catalysis, yet very challenging. Chiral MOFs with MOF-74 topology were synthesised by using post-synthetic modification with proline. Vibrational circular dichroism studies demonstrate that proline is the source of chirality. The solvents used in the synthesis play a key role in tuning the loading of proline and its interaction with the MOF-74 framework. In N,N'-dimethylformamide, proline coordinates monodentate to the Zn 2+ ions within the MOF-74 framework, whereas it is only weakly bound to the framework when using methanol as solvent. Introducing chirality within the MOF-74 framework also leads to the formation of defects, with both the organic linker and metal ions missing from the framework. The formation of defects combined with the coordination of DMF and proline within the framework leads to a pore blocking effect. This is confirmed by adsorption studies and testing of the chiral MOFs in the asymmetric aldol reaction between acetone and para-nitrobenzaldehyde., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

An AlPO 4 zeotype has been prepared using the aromatic diamine 1,10-phenanthroline and some of its methylated analogues as templates. In each case the two template N atoms bind to a specific framework Al site to expand its coordination to the unusual octahedral AlO 4 N 2 environment. Furthermore, using this framework-bound template, Fe atoms can be included selectively at this site in the framework by direct synthesis, as confirmed by annular dark field scanning transmission electron microscopy and Rietveld refinement. Calcination removes the organic molecules to give large pore framework solids, with BET surface areas up to 540 m 2  g -1 and two perpendicular sets of channels that intersect to give pore space connected by 12-ring openings along all crystallographic directions., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

We present an NMR crystallographic investigation of two as-made forms of the recently characterized gallophosphate GaPO-34A, which has an unusual framework composition with a Ga:P ratio of 7:6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional, and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of five of these, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71 Ga NMR spectroscopy and variable-temperature 13 C and 31 P NMR experiments shows that the structure directing agents are dynamic on the microsecond time scale, which can be supported by averaging the 31 P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present.

The breathing behaviour of 17O-enriched (Al,Ga)-MIL-53, a terephthalate-based metal-organic framework, has been investigated using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction (PXRD) and first-principles calculations. These reveal that the behaviour observed for as-made, calcined, hydrated and subsequently dehydrated mixed-metal MIL-53 materials differs with composition, but cannot be described as the compositionally weighted average of the breathing behaviour seen for the two end members. Although the form of MIL-53 adopted by the as-made material is independent of metal composition, upon calcination, materials with higher levels of Al adopt an open pore (OP) form, as found for the Al end member, but substitution of Ga results in mixed pore materials, with OP and narrow pore (NP) forms co-existing. Although the Ga end member is prone to decomposition under the calcination conditions used, a low level of Al in the starting synthesis (5%) leads to an OP mixed-metal MOF that is stable to calcination. Upon hydration, all materials almost exclusively adopt a closed pore (CP) structure, with strong hydrogen bonding interactions with water leading to two distinct resonances from the carboxylate oxygens in 17O NMR spectra. When dehydrated, different framework structures are found for the two end members, OP for Al-MIL-53 and NP for Ga-MIL-53, with the proportion of NP MOF seen to increase systematically with the Ga content in mixed-metal materials, in contrast to the forms seen upon initial calcination. 17O NMR spectra of mixed-metal MIL-53 materials show an increased preference for clustering of like cations as the Ga content increases. This is not a result of the small-scale dry gel conversion reactions used for enrichment, as a similar cation distribution and clustering is also observed for (Al0.5,Ga0.5)-MIL-53 synthesised hydrothermally and enriched with 17O via post-synthetic steaming.

The ADOR (Assembly-Disassembly-Organisation-Reassembly) process for zeolites has been shown to produce a number of previously unknown frameworks inaccessible through conventional synthesis methods. Here, we present successful mechanochemically assisted hydrolysis of germanosilicate zeolite UTL leading to ADOR products under mild conditions, low amounts of solvent and in short reaction times. The expansion of zeolite synthesis into the realm of mechanochemistry opens up feasible pathways regarding the production of these materials, especially for industrial purposes, as well as an exciting application for economical enrichment of materials with the low natural abundance NMR-active isotope of oxygen, 17 O. The results from mechanochemically assisted hydrolysis differ from those seen in the traditional ADOR approach: differences that can be attributed to a change in solvent availability., (This journal is © The Royal Society of Chemistry 2020.)

A series of acenaphthene species with a diisopropylphosphino group and a variety of bismuth functionalities in the peri positions were synthesized and fully characterized, including single-crystal X-ray diffraction. The majority of the reported species feature a relatively rare interpnictogen P-Bi bond. The series includes the phosphine-bismuthine Acenap(P i Pr 2 )(BiPh 2 ) ( 2 ; Acenap = acenaphthene-5,6-diyl), which was subjected to a fluorodearylation reaction to produce Acenap(P i Pr 2 )(BiPhX) ( 5 - 8 and 10 ; X = BF 4 - , Cl, Br, I, SPh), displaying varying degrees of ionicity. The geminally bis(acenaphthyl)-substituted [Acenap(P i Pr 2 )] 2 BiPh ( 3 ) shows a large through-space coupling of 17.8 Hz, formally 8TS J PP . Coupling deformation density calculations confirm the double through-space coupling pathway, in which the P and Bi lone pairs mediate communication between the two 31 P nuclei. Several synthetic routes toward the phosphine-diiodobismuthine Acenap(P i Pr 2 )(BiI 2 ) ( 9 ) have been investigated; however, the purity of this, surprisingly thermally stable potential synthon, remains poor.

The synthesis of a new solid solution of the oxyhydroxide Ga 5- x Al x O 7 (OH) is investigated via solvothermal reaction between gallium acetylacetonate and aluminum isopropoxide in 1,4-butanediol at 240 °C. A limited compositional range of 0 ≤ x ≤ 1.5 is produced, with the hexagonal unit cell parameters refined from powder X-ray diffraction (XRD) showing a linear contraction in unit cell volume with an increase in Al content. Solid-state 27 Al and 71 Ga nuclear magnetic resonance (NMR) spectroscopies show a strong preference for Ga to occupy the tetrahedral sites and Al to occupy the octahedral sites. Using isopropanol as the solvent, γ-Ga 2- x Al x O 3 defect spinel solid solutions with x ≤ 1.8 can be prepared at 240 °C in 24 h. These materials are nanocrystalline, as evidenced by their broad diffraction profiles; however, the refined cubic lattice parameter shows a linear relationship with the Ga:Al content, and solid-state NMR spectroscopy again shows a preference for Al to occupy the octahedral sites. Thermal decomposition of Ga 5- x Al x O 7 (OH) occurs via poorly ordered materials that resemble ε-Ga 2- x Al x O 3 and κ-Ga 2- x Al x O 3 , but γ-Ga 2- x Al x O 3 transforms above 750 °C to monoclinic β-Ga 2- x Al x O 3 for 0 ≤ x ≤ 1.3 and to hexagonal α-Ga 2- x Al x O 3 for x = 1.8, with intermediate compositions of 1.3 < x < 1.8 giving mixtures of the α- and β-polymorphs. Solid-state NMR spectroscopy shows only the expected octahedral Al for α-Ga 2- x Al x O 3 , and for β-Ga 2- x Al x O 3 , the ∼1:2 tetrahedral:octahedral Al ratio is in good agreement with the results of Rietveld analysis of the average structures against powder XRD data. Relative energies calculated by periodic density functional theory confirm that there is an ∼5.2 kJ mol -1 penalty for tetrahedral rather than octahedral Al in Ga 5- x Al x O 7 (OH), whereas this penalty is much smaller (∼2.0 kJ mol -1 ) for β-Ga 2- x Al x O 3 , in good qualitative agreement with the experimental NMR spectra.

A new approach for room-temperature 17 O enrichment of zeolites reveals a surprisingly dynamic and labile framework, where rapid and reversible bond breaking takes place. 17 O NMR spectroscopy shows that although O sites in both framework Si-O-Al and Si-O-Si linkages are enriched simply on exposure to H 2 17 O(l), the enrichment of Si-O-Al species is more rapid, with a more uniform framework enrichment observed at longer durations. We demonstrate that this unexpected enrichment can be observed for two different framework topologies and for Na-exchanged (i.e., nonacidic) zeolites, as well as their protonic forms, confirming that the Brønsted acid proton is not necessary for isotopic exchange into the framework. This work not only offers new opportunities for structural characterization of these chemically and industrially important materials using NMR spectroscopy but suggests that further investigation of the rate and position of enrichment in zeolite frameworks could provide new insight into their chemical reactivity and their stability in aqueous-based applications such as ion exchange and catalysis.

The sensitivity of NMR to the local environment, without the need for any long-range order, makes it an ideal tool for the characterization of disordered materials. Computational prediction of NMR parameters can be of considerable help in the interpretation and assignment of NMR spectra of solids, but the statistical representation of all possible chemical environments for a solid solution is challenging. Here, we illustrate the use of a symmetry-adapted configurational ensemble in the simulation of NMR spectra, in combination with solid-state NMR experiments. We show that for interpretation of the complex and overlapped lineshapes that are typically observed, it is important to go beyond a single-configuration representation or a simple enumeration of local environments. The ensemble method leads to excellent agreement between simulated and experimental spectra for Y 2 (Sn,Ti) 2 O 7 pyrochlore ceramics, where the overlap of signals from different local environments prevents a simple decomposition of the experimental spectral lineshapes. The inclusion of a Boltzmann weighting confirms that the best agreement with experiment is obtained at higher temperatures, in the limit of full disorder. We also show that to improve agreement with experiment, in particular at low dopant concentrations, larger supercells are needed, which might require alternative simulation approaches as the complexity of the system increases. It is clear that ensemble-based modeling approaches in conjunction with NMR spectroscopy offer great potential for understanding configurational disorder, ultimately aiding the future design of functional materials.

Aluminosilicate zeolites are traditionally used in high-temperature applications at low water vapour pressures where the zeolite framework is generally considered to be stable and static. Increasingly, zeolites are being considered for applications under milder aqueous conditions. However, it has not yet been established how neutral liquid water at mild conditions affects the stability of the zeolite framework. Here, we show that covalent bonds in the zeolite chabazite (CHA) are labile when in contact with neutral liquid water, which leads to partial but fully reversible hydrolysis without framework degradation. We present ab initio calculations that predict novel, energetically viable reaction mechanisms by which Al-O and Si-O bonds rapidly and reversibly break at 300 K. By means of solid-state NMR, we confirm this prediction, demonstrating that isotopic substitution of 17 O in the zeolitic framework occurs at room temperature in less than one hour of contact with enriched water.

NMR spectroscopy of paramagnetic materials (pNMR) has the potential to provide great structural insight, but many challenges remain in interpreting the spectra in detail. This work presents a study of a series of structurally analogous metal-organic frameworks (MOFs) based on 5-substituted isophthalate linkers and Cu(II) paddlewheel dimers, of interest owing to their "crumple zone" structural rearrangement on dehydration/rehydration. 13 C MAS NMR spectra reveal a wide variation in the observed resonance position for chemically similar C species in the different MOFs but, despite this, resonances are overlapped in several cases. However, by considering a combination of the integration of quantitative spectra, the resonance position as a function of temperature and T 1 relaxation measurements, the spectra can be fully assigned. It is also demonstrated that the prototypical MOF in this series, STAM-1, displays a crumple zone rearrangement on dehydration, similar to the well-characterised 5-ethoxyisophthalate MOF (STAM-17-OEt) although, while the materials have similar local C environments, dehydrated STAM-1 exhibits less long-range order., (Copyright © 2019 Elsevier Inc. All rights reserved.)

We report solid-state 13 C NMR spectra of urea-loaded copper benzoate, Cu 2 (C 6 H 5 CO 2 ) 4 ·2(urea), a simplified model for copper paddlewheel-based metal-organic frameworks (MOFs), along with first-principles density functional theory (DFT) computation of the paramagnetic NMR (pNMR) chemical shifts. Assuming a Boltzmann distribution between a diamagnetic open-shell singlet ground state (in a broken-symmetry Kohn-Sham DFT description) and an excited triplet state, the observed δ( 13 C) values are reproduced reasonably well at the PBE0-⅓/IGLO-II//PBE0-D3/AE1 level. Using the proposed assignments of the signals, the mean absolute deviation between computed and observed 13 C chemical shifts is below 30 ppm over a range of more than 1100 ppm., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The multiple-quantum magic-angle spinning (MQMAS) experiment is a popular choice for obtaining high-resolution solid-state NMR spectra of quadrupolar nuclei with half-integer spin quantum number. However, its inherently poor sensitivity limits its application in more challenging systems. In particular, the use of higher-order multiple-quantum coherences, which have the potential to provide higher resolution in the isotropic spectrum, results in a further decrease in sensitivity. Here we extend our recent work, which introduced an automated, high-throughput approach to generate amplitude-modulated composite pulses (termed FAM-N) to improve the efficiency of the conversion of three-quantum coherences, and explore the use of similar pulses in five-quantum MAS experiments. We consider three different approaches, and are able to demonstrate that all three provide good enhancements over single pulse conversion in all but the most extreme cases, and work well at a range of spinning rates. We show that FAM-N pulses are robust to variation in the quadrupolar coupling and rf nutation rate, demonstrating their applicability in multisite systems and systems where direct experimental optimisation of complex composite pulses is not feasible. This work will ease the implementation of higher-order MQMAS experiments and enable their application to materials and systems that were previously deemed too difficult to study., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

In this paper we undertake a study of the decoupling efficiency of the Multiple-Pulse (MP) scheme, and a rationalization of its parameterization and of the choice of instrumental set up. This decoupling scheme is known to remove the broadening of spin-1/2 spectra I, produced by the heteronuclear scalar interaction with a half-integer quadrupolar nucleus S, without reintroducing heteronuclear dipolar interaction. The resulting resolution enhancement depends on the set-up of the length of the series of pulses and delays of the MP, and some intrinsic material and instrumental parameters. Firstly through a numerical approach, this study investigates the influence of the main intrinsic material parameters (heteronuclear dipolar and J coupling, quadrupolar interaction, spin nature) and instrumental parameters (spinning rate, pulse field strength) on efficiency and resolution enhancement of the scalar decoupling scheme. A guideline is then proposed to obtain quickly and easily the best resolution enhancement via the rationalization of the instrumental and parameter set up. It is then illustrated and tested through experimental data, probing the efficiency of MP-decoupling set up using this guideline. Various spin systems were tested ( 31 P- 51 V in VOPO 4 , 31 P- 93 Nb in NbOPO 4 , 119 Sn- 17 O in Y 2 Sn 2 O 7 ), combined with simulations results., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The 31 P chemical shift anisotropy (CSA) offers a potential source of new information to help determine the structures of aluminophosphate (AlPO) framework materials. We investigate how to measure the CSAs, which are small (span of ~20-30 ppm) for AlPOs, demonstrating the need for CSA-amplification experiments (often in conjunction with 27 Al and/or 1 H decoupling) at high magnetic field (20.0 T) to obtain accurate values. We show that the most shielded component of the chemical shift tensor, δ 33 , is related to the length of the shortest P─O bond, whereas the more deshielded components, δ 11 and δ 22 can be related more readily to the mean P─O bond lengths and P─O─Al angles. Using the case of Mg-doped STA-2 as an example, the CSA is shown to be much larger for P(OAl) 4-n (OMg) n environments, primarily owing to a much shorter P─O(Mg) bond affecting δ 33 , however, because the mean P─O bond lengths and P─O─T (T = Al, Mg) bond angles do not change significantly between P(OAl) 4 and P(OAl) 4-n (OMg) n sites, the isotropic chemical shifts for these species are similar, leading to overlapped spectral lines. When the CSA information is included, spectral assignment becomes unambiguous, therefore, although the specialist conditions required might preclude the routine measurement of 31 P CSAs in AlPOs, in some cases (particularly doped materials), the experiments can still provide valuable additional information for spectral assignment., (© 2018 John Wiley & Sons, Ltd.)

An unambiguous crystallographic structure solution for the observed phases II-VI of high pressure hydrogen does not exist due to the failure of standard structural probes at extreme pressure. In this work we propose that nuclear magnetic resonance spectroscopy provides a complementary structural probe for high pressure hydrogen. We show that the best structural models available for phases II, III, and IV of high pressure hydrogen exhibit markedly distinct nuclear magnetic resonance spectra which could therefore be used to discriminate amongst them. As an example, we demonstrate how nuclear magnetic resonance spectroscopy could be used to establish whether phase III exhibits polymorphism. Our calculations also reveal a strong renormalization of the nuclear magnetic resonance response in hydrogen arising from quantum fluctuations, as well as a strong isotope effect. As the experimental techniques develop, nuclear magnetic resonance spectroscopy can be expected to become a useful complementary structural probe in high pressure experiments.

The hydrolysis (disassembly, D) and rearrangement (organization, O) steps of the assembly-disassembly-organization-reassembly (ADOR) process for the synthesis of zeolites have been studied. Germanium-rich UTL was subjected to hydrolysis conditions in water to understand the effects of temperature (100, 92, 85, 81, 77, and 70 °C). Samples were taken periodically over an 8-37 h period, and each sample was analyzed by powder X-ray diffraction. The results show that the hydrolysis step is solely dependent on the presence of liquid water, whereas the rearrangement is dependent on the temperature of the system. The kinetics have been investigated using the Avrami-Erofeev model. With increasing temperature, an increase in the rate of reaction for the rearrangement step was observed, and the Arrhenius equation was used to ascertain an apparent activation energy for the rearrangement from the kinetic product of the disassembly (IPC-1P) to the thermodynamic product of the rearrangement (IPC-2P). From this information, a mechanism for this transformation can be postulated.

High-silica zeolites, some of the most important and widely used catalysts in industry, have potential for application across a wide range of traditional and emerging technologies. The many structural topologies of zeolites have a variety of potential uses, so a strong drive to create new zeolites exists. Here, we present a protocol, the assembly-disassembly-organization-reassembly (ADOR) process, for a relatively new method of preparing these important solids. It allows the synthesis of new high-silica zeolites (Si/Al >1,000), whose synthesis is considered infeasible with traditional (solvothermal) methods, offering new topologies that may find novel applications. We show how to identify the optimal conditions (e.g., duration of reaction, temperature, acidity) for ADOR, which is a complex process with different possible outcomes. Following the protocol will allow researchers to identify the different products that are possible from a reaction without recourse to repetitive and time-consuming trial and error. In developing the protocol, germanium-containing UTL zeolites were subjected to hydrolysis conditions using both water and hydrochloric acid as media, which provides an understanding of the effects of temperature and pH on the disassembly (D) and organization (O) steps of the process that define the potential products. Samples were taken from the ongoing reaction periodically over a minimum of 8 h, and each sample was analyzed using powder X-ray diffraction to yield a time course for the reaction at each set of conditions; selected samples were analyzed using transmission electron microscopy and solid-state NMR spectroscopy.

The Earth's transition zone, at depths of 410-660 km, while being composed of nominally anhydrous magnesium silicate minerals, may be subject to significant hydration. Little is known about the mechanism of hydration, despite the vital role this plays in the physical and chemical properties of the mantle, leading to a need for improved structural characterization. Here we present an ab initio random structure searching (AIRSS) investigation of semihydrous (1.65 wt % H 2 O) and fully hydrous (3.3 wt % H 2 O) wadsleyite. Following the AIRSS process, k-means clustering was used to select sets of structures with duplicates removed, which were then subjected to further geometry optimization with tighter constraints prior to NMR calculations. Semihydrous models identify a ground-state structure (Mg3 vacancies, O1-H hydroxyls) that aligns with a number of previous experimental observations. However, predicted NMR parameters fail to reproduce low-intensity signals observed in solid-state NMR spectra. In contrast, the fully hydrous models produced by AIRSS, which enable both isolated and clustered defects, are able to explain observed NMR signals via just four low-enthalpy structures: (i) a ground state, with isolated Mg3 vacancies and O1-H hydroxyls; (ii/iii) edge-sharing Mg3 vacancies with O1-H and O3-H species; and (iv) edge-sharing Mg1 and Mg3 vacancies with O1-H, O3-H, and O4-H hydroxyls. Thus, the combination of advanced structure searching approaches and solid-state NMR spectroscopy is able to provide new and detailed insight into the structure of this important mantle mineral.

Soluble additives provide a versatile strategy for controlling crystallization processes, enabling selection of properties including crystal sizes, morphologies, and structures. The additive species can also be incorporated within the crystal lattice, leading for example to enhanced mechanical properties. However, while many techniques are available for analyzing particle shape and structure, it remains challenging to characterize the structural inhomogeneities and defects introduced into individual crystals by these additives, where these govern many important material properties. Here, we exploit Bragg coherent diffraction imaging to visualize the effects of soluble additives on the internal structures of individual crystals on the nanoscale. Investigation of bio-inspired calcite crystals grown in the presence of lysine or magnesium ions reveals that while a single dislocation is observed in calcite crystals grown in the presence of lysine, magnesium ions generate complex strain patterns. Indeed, in addition to the expected homogeneous solid solution of Mg ions in the calcite lattice, we observe two zones comprising alternating lattice contractions and relaxation, where comparable alternating layers of high magnesium calcite have been observed in many magnesium calcite biominerals. Such insight into the structures of nanocomposite crystals will ultimately enable us to understand and control their properties.

Highly porous metal-organic frameworks (MOFs), which have undergone exciting developments over the past few decades, show promise for a wide range of applications. However, many studies indicate that they suffer from significant stability issues, especially with respect to their interactions with water, which severely limits their practical potential. Here we demonstrate how the presence of 'sacrificial' bonds in the coordination environment of its metal centres (referred to as hemilability) endows a dehydrated copper-based MOF with good hydrolytic stability. On exposure to water, in contrast to the indiscriminate breaking of coordination bonds that typically results in structure degradation, it is non-structural weak interactions between the MOF's copper paddlewheel clusters that are broken and the framework recovers its as-synthesized, hydrated structure. This MOF retained its structural integrity even after contact with water for one year, whereas HKUST-1, a compositionally similar material that lacks these sacrificial bonds, loses its crystallinity in less than a day under the same conditions.

Post-synthetic modification of the hafnium metal-organic framework MOF-808(Hf) to include triarylphosphine ligands is reported. Sulfonated phenylphosphines are incorporated without oxidation to give a "MOF ligand" that can complex late transition metals such as Ir and Rh to give a bifunctional catalyst containing both metal-phosphine complexes and the Lewis acidic framework hafnium metal sites. The metallated phosphine-bearing MOFs act as fully heterogeneous bifunctional catalysts for tandem reductive amination and hydroaminomethylation reactions., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The rhodium(III) hydrogarnets Ca 3 Rh 2 (OH) 12 and Sr 3 Rh 2 (OH) 12 crystallize as polycrystalline powders under hydrothermal conditions at 200 °C from RhCl 3 ·3H 2 O and either Ca(OH) 2 or Sr(OH) 2 in either 12 M NaOH or KOH. Rietveld refinements against synchrotron powder X-ray diffraction (XRD) data allow the first crystal structures of the two materials to be determined. If BaO 2 is used as a reagent and the concentration of hydroxide increased to hydroflux conditions (excess NaOH), then single crystals of a new complex rhodium hydroxide, BaNaRh(OH) 6 , are formed in a phase-pure sample, with sodium included from the flux. Structure solution from single-crystal XRD data reveals isolated octahedral Rh centers that share hydroxides with 10-coordinate Ba and two independent 8-coordinate Na sites. 23 Na magic-angle spinning NMR confirms the presence of the two crystallographically distinct Na sites and also verifies the diamagnetic nature of the sample, expected for Rh(III). The thermal behavior of the hydroxides on heating in air was investigated using X-ray thermodiffractometry, showing different decomposition pathways for each material. Ca 3 Rh 2 (OH) 12 yields CaRh 2 O 4 and CaO above 650 °C, from which phase-pure CaRh 2 O 4 is isolated by washing with dilute nitric acid, a material previously only reported by high-pressure or high-temperature synthesis. Sr 3 Rh 2 (OH) 12 decomposes to give a less crystalline material with a powder XRD pattern that is matched to the 2H-layered hexagonal perovskite Sr 6 Rh 5 O 15 , which contains mixed-valent Rh 3+/4+ , confirmed by Rh K-edge XANES spectroscopy. On heating BaNaRh(OH) 6 , a complex set of decomposition events takes place via transient phases.