The Interplay of Electronic Configuration and Anion Ordering on the Magnetic Behavior of Hydroxyfluoride Diaspores.

We report a new nickel hydroxyfluoride diaspore Ni(OH)F prepared using hydrothermal synthesis from NiCl2·6H2O and NaF. Magnetic characterization reveals that, contrary to other reported transition-metal hydroxyfluoride diaspores, Ni(OH)F displays weak ferromagnetism below the magnetic ordering temperature. To understand this difference, neutron diffraction is used to determine the long-range magnetic structure. The magnetic structure is found to be distinct from those reported for other hydroxyfluoride diaspores and shows an antiferromagnetic spin ordering in which ferromagnetic canting is allowed by symmetry. Furthermore, neutron powder diffraction on a deuterated sample, Ni(OD)F, reveals partial anion ordering that is distinctive to what has previously been reported for Co(OH)F and Fe(OH)F. Density functional theory calculations show that OH/F ordering can have a directing influence on the lowest energy magnetic ground state. Our results point toward a subtle interplay between the sign of magnetic exchange interactions, the electronic configuration, and anion disordering.

Limits of Solid Solution and Evolution of Crystal Morphology in (La1-xREx)FeO3 Perovskites by Low Temperature Hydrothermal Crystallization.

The crystallization of a new series of A-site substituted lanthanum ferrite materials (La1-xREx)FeO3 was explored by the hydrothermal method at 240 °C, for rare earth (RE) = Nd, Sm, Gd, Ho, Er, Yb, and Y, with 0 ≤ x ≤ 1. The effect of elemental substitution on the morphological, structural, and magnetic properties of the materials was studied using high-resolution powder X-ray diffraction, energy dispersive spectroscopy (EDS) on the scanning electron microscope, Raman spectroscopy, and SQUID magnetometry. If the radius of the La3+ and the substituent ions is similar, such as for Nd3+, Sm3+, and Gd3+, homogeneous solid solutions are formed, with the orthorhombic GdFeO3-type structure, and a continuous evolution of Raman spectra with composition and distinct magnetic behavior from the end members. When the radius difference between substituents and La3+ is large, such as for Ho3+, Er3+, Yb3+, and Y3+, then instead of forming solid solutions, crystallization in separate phases is found. However, low levels of element mixing are found and intergrowths of segregated regions give composite particles. In this case, the Raman spectra and magnetic behavior are characteristic of mixtures of phases, while EDS shows distinctive elemental segregation. A-site replacement induces an evolution in the crystallite shape with an increasing amount of substituent ions and this is most evident for RE = Y from cube-shaped crystals seen for LaFeO3 to multipodal crystals for (La1-xYx)FeO3, providing evidence for a phase-separation-driven evolution of morphology.

The Influence of Defects on the Luminescence of Trivalent Terbium in Nanocrystalline Yttrium Orthovanadate.

Terbium-doped YVO4 has been considered a nonluminescent solid since the first classic studies on rare-earth-doped phosphors in the 1960s. However, we demonstrate that defect engineering of YVO4:Tb3+ nanoparticles overcomes the metal-metal charge transfer (MMCT) process which is responsible for the quenching of the Tb3+ luminescence. Tetragonal (Y1-xTbx)VO4 nanoparticles obtained by colloidal precipitation showed expanded unit cells, high defect densities, and intimately mixed carbonates and hydroxides, which contribute to a shift of the MMCT states to higher energies. Consequently, we demonstrate unambiguously for the first time that Tb3+ luminescence can be excited by VO43- → Tb3+ energy transfer and by direct population of the 5D4 state in YVO4. We also discuss how thermal treatment removes these effects and shifts the quenching MMCT state to lower energies, thus highlighting the major consequences of defect density and microstructure in nanosized phosphors. Therefore, our findings ultimately show nanostructured YVO4:Tb3+ can be reclassified as a UV-excitable luminescent material.

A Highly Stable Yttrium Organic Framework as a Host for Optical Thermometry and D2 O Detection.

The yttrium organic framework (Y0.89 Tb0.10 Eu0.01 )6 (BDC)7 (OH)4 (H2 O)4 (BDC=benzene-1,4-dicarboxylate) is hydrothermally stable up to at least 513 K and thermally stable in air in excess of 673 K. The relative intensities of luminescence of Tb3+ and Eu3+ are governed by Tb3+ -to-Eu3+ phonon-assisted energy transfer and Tb3+ -to-ligand back transfer and are responsible for the differing temperature-dependent luminescence of the two ions. This provides a ratiometric luminescent thermometer in the 288-573 K temperature range, not previously seen for MOF materials, with a high sensitivity, 1.69±0.04 % K-1 at 523 K. In aqueous conditions, loosely bound H2 O can be replaced by D2 O in the same material, which modifies decay lifetimes to yield a quantitative luminescent D2 O sensor with a useful sensitivity for practical application.

Nonredox CO2 Fixation in Solvent-Free Conditions Using a Lewis Acid Metal-Organic Framework Constructed from a Sustainably Sourced Ligand.

CO2 epoxidation to cyclic carbonates under mild, solvent-free conditions is a promising pathway toward sustainable CO2 utilization. Metal-organic frameworks (MOFs) explored for such applications so far are commonly composed of nonrenewable ligands such as benzene dicarboxylate (BDC) or synthetically complex linkers and therefore are not suitable for commercial utilization. Here, we report new yttrium 2,5-furandicarboxylate (FDC)-based MOFs: "UOW-1" and "UOW-2" synthesized via solvothermal assembly, with the former having a unique structural topology. The FDC linker can be derived from biomass and is a green and sustainable alternative to conventionally used BDC ligands, which are sourced exclusively from fossil fuels. UOW-1, owing to unique coordination unsaturation and a high density of Lewis active sites, promotes a high catalytic activity (∼100% conversion; ∼99% selectivity), a high turnover frequency (70 h-1), and favorable first-order kinetics for CO2 epoxidation reactions using an epichlorohydrin model substrate under solvent-free conditions within 6 h and a minimal cocatalyst amount. A systematic catalytic study was carried out by broadening the epoxide substrate scope to determine the influence of electronic and steric factors on CO2 epoxidation. Accordingly, higher conversion efficiencies were observed for substrates with high electrophilicity on the carbon center and minimal steric bulk. The work presents the first demonstration of sustainable FDC-based MOFs used for efficient CO2 utilization.

Perovskite Oxides Prepared by Hydrothermal and Solvothermal Synthesis: A Review of Crystallisation, Chemistry, and Compositions.

Perovskite oxides with general composition ABO3 are a large group of inorganic materials that can contain a variety of cations from all parts of the Periodic Table and that have diverse properties of application in fields ranging from electronics, energy storage to photocatalysis. Solvothermal synthesis routes to these materials have become increasingly investigated in the past decade as a means of direct crystallisation of the solids from solution. These methods have significant advantages leading to adjustment of crystal form from the nanoscale to the micron-scale, the isolation of compositions not possible using conventional solid-state synthesis and in addition may lead to scalable processes for producing materials at moderate temperatures. These aspects are reviewed, with examples taken from the past decade's literature on the solvothermal synthesis of perovskites with a systematic survey of B-site cations, from transition metals in Groups 4-8 and main group elements in Groups 13, 14 and 15, to solid solutions and heterostructures. As well as hydrothermal reactions, the use of various solvents and solution additives are discussed and some trends identified, along with prospects for developing control and predictability in the crystallisation of complex oxide materials.

Synthesis and Polymorphism of Mixed Aluminum-Gallium Oxides.

The synthesis of a new solid solution of the oxyhydroxide Ga5-xAlxO7(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 27Al and 71Ga 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-Ga2-xAlxO3 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 Ga5-xAlxO7(OH) occurs via poorly ordered materials that resemble ε-Ga2-xAlxO3 and κ-Ga2-xAlxO3, but γ-Ga2-xAlxO3 transforms above 750 °C to monoclinic ß-Ga2-xAlxO3 for 0 ≤ x ≤ 1.3 and to hexagonal α-Ga2-xAlxO3 for x = 1.8, with intermediate compositions of 1.3 < x < 1.8 giving mixtures of the α- and ß-polymorphs. Solid-state NMR spectroscopy shows only the expected octahedral Al for α-Ga2-xAlxO3, and for ß-Ga2-xAlxO3, 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 Ga5-xAlxO7(OH), whereas this penalty is much smaller (∼2.0 kJ mol-1) for ß-Ga2-xAlxO3, in good qualitative agreement with the experimental NMR spectra.

Application of NMR Crystallography to Highly Disordered Templated Materials: Extensive Local Structural Disorder in the Gallophosphate GaPO-34A.

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 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond time scale, which can be supported by averaging the 31P 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.

In situ XAFS of acid-resilient iridate pyrochlore oxygen evolution electrocatalysts under operating conditions.

Pyrochlore iridates (Na,Ca)2-xIr2O6·H2O are acid-stable electrocatalysts that are candidates for use in electrolysers and fuel cells. Ir LIII-edge X-ray absorption fine structure spectroscopy in 1 M H2SO4 at oxygen evolution conditions suggests the involvement of the electrons from the conduction band of the metallic particles, rather than just surface iridium reacting.

Investigating discrepancies between experimental solid-state NMR and GIPAW calculation: NC-N 13C and OH⋯O 1H chemical shifts in pyridinium fumarates and their cocrystals.

An NMR crystallography analysis is presented for four solid-state structures of pyridine fumarates and their cocrystals, using crystal structures deposited in the Cambridge Crystallographic Data Centre, CCDC. Experimental one-dimensional one-pulse 1H and 13C cross-polarisation (CP) magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and two-dimensional 14N-1H heteronuclear multiple-quantum coherence MAS NMR spectra are compared with gauge-including projector augmented wave (GIPAW) calculations of the 1H and 13C chemical shifts and the 14N shifts that additionally depend on the quadrupolar interaction. Considering the high ppm (>10 â€‹ppm) 1H resonances, while there is good agreement (within 0.4 â€‹ppm) between experiment and GIPAW calculation for the hydrogen-bonded NH moieties, the hydrogen-bonded fumaric acid OH resonances are 1.2-1.9 â€‹ppm higher in GIPAW calculation as compared to experiment. For the cocrystals of a salt and a salt formed by 2-amino-5-methylpyridinium and 2-amino-6-methylpyridinium ions, a large discrepancy of 4.2 and 5.9 â€‹ppm between experiment and GIPAW calculation is observed for the quaternary ring carbon 13C resonance that is directly bonded to two nitrogens (in the ring and in the amino group). By comparison, there is excellent agreement (within 0.2 â€‹ppm) for the quaternary ring carbon 13C resonance directly bonded to the ring nitrogen for the salt and cocrystal of a salt formed by 2,6-lutidinium and 2,5-lutidinium, respectively.

5-amino-2-methylpyridinium hydrogen fumarate: An XRD and NMR crystallography analysis.

Single-crystal X-ray diffraction structures of the 5-amino-2-methylpyridinium hydrogen fumarate salt have been solved at 150 and 300 K (CCDC 1952142 and 1952143). A base-acid-base-acid ring is formed through pyridinium-carboxylate and amine-carboxylate hydrogen bonds that hold together chains formed from hydrogen-bonded hydrogen fumarate ions. 1 H and 13 C chemical shifts as well as 14 N shifts that additionally depend on the quadrupolar interaction are determined by experimental magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) and gauge-including projector-augmented wave (GIPAW) calculation. Two-dimensional homonuclear 1 H-1 H double-quantum (DQ) MAS and heteronuclear 1 H-13 C and 14 N-1 H spectra are presented. Only small differences of up to 0.1 and 0.6 ppm for 1 H and 13 C are observed between GIPAW calculations starting with the two structures solved at 150 and 300 K (after geometry optimisation of atomic positions, but not unit cell parameters). A comparison of GIPAW-calculated 1 H chemical shifts for isolated molecules and the full crystal structures is indicative of hydrogen bonding strength.

Electric Field-Controlled Synthesis and Characterisation of Single Metal-Organic-Framework (MOF) Nanoparticles.

Achieving control over the size distribution of metal-organic-framework (MOF) nanoparticles is key to biomedical applications and seeding techniques. Electrochemical control over the nanoparticle synthesis of the MOF, HKUST-1, is achieved using a nanopipette injection method to locally mix Cu2+ salt precursor and benzene-1,3,5-tricarboxylate (BTC3- ) ligand reagents, to form MOF nanocrystals, and collect and characterise them on a TEM grid. In situ analysis of the size and translocation frequency of HKUST-1 nanoparticles is demonstrated, using the nanopipette to detect resistive pulses as nanoparticles form. Complementary modelling of mass transport in the electric field, enables particle size to be estimated and explains the feasibility of particular reaction conditions, including inhibitory effects of excess BTC3- . These new methods should be applicable to a variety of MOFs, and scaling up synthesis possible via arrays of nanoscale reaction centres, for example using nanopore membranes.

Pair Distribution Function Analysis of Structural Disorder by Nb5+ Inclusion in Ceria: Evidence for Enhanced Oxygen Storage Capacity from Under-Coordinated Oxide.

Partial substitution of Ce4+ by Nb5+ is possible in CeO2 by coinclusion of Na+ to balance the charge, via hydrothermal synthesis in sodium hydroxide solution. Pair distribution function analysis using reverse Monte Carlo refinement reveals that the small pentavalent substituent resides in irregular coordination positions in an average fluorite lattice, displaced away from the ideal cubic coordination toward four oxygens. This results in under-coordinated oxygen, which explains significantly enhanced oxygen storage capacity of the materials of relevance to redox catalysis used in energy and environmental applications.

Monitoring the Hydrothermal Growth of Cobalt Spinel Water Oxidation Catalysts: From Preparative History to Catalytic Activity.

The hydrothermal growth of cobalt oxide spinel (Co3 O4 ) nanocrystals from cobalt acetate precursors was monitored with in situ powder X-ray diffraction (PXRD) in combination with ex situ electron microscopy and vibrational spectroscopy. Kinetic data from in situ PXRD monitoring were analyzed using Sharp-Hancock and Gualtieri approaches, which both clearly indicate a change of the growth mechanism for reaction temperatures above 185 °C. This mechanistic transition goes hand in hand with morphology changes that notably influence the photocatalytic oxygen evolution activity. Complementary quenching investigations of conventional hydrothermal Co3 O4 growth demonstrate that these insights derived from in situ PXRD data provide valuable synthetic guidelines for water oxidation catalyst production. Furthermore, the ex situ analyses of hydrothermal quenching experiments were essential to assess the influence of amorphous cobalt-containing phases arising from the acetate precursor on the catalytic activity. Thereby, the efficient combination of a single in situ technique with ex situ analyses paves the way to optimize parameter-sensitive hydrothermal production processes of key energy materials.

Alkaline-Earth Rhodium Hydroxides: Synthesis, Structures, and Thermal Decomposition to Complex Oxides.

The rhodium(III) hydrogarnets Ca3Rh2(OH)12 and Sr3Rh2(OH)12 crystallize as polycrystalline powders under hydrothermal conditions at 200 °C from RhCl3·3H2O 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 BaO2 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. 23Na 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. Ca3Rh2(OH)12 yields CaRh2O4 and CaO above 650 °C, from which phase-pure CaRh2O4 is isolated by washing with dilute nitric acid, a material previously only reported by high-pressure or high-temperature synthesis. Sr3Rh2(OH)12 decomposes to give a less crystalline material with a powder XRD pattern that is matched to the 2H-layered hexagonal perovskite Sr6Rh5O15, which contains mixed-valent Rh3+/4+, confirmed by Rh K-edge XANES spectroscopy. On heating BaNaRh(OH)6, a complex set of decomposition events takes place via transient phases.

23-Electron Octahedral Molybdenum Cluster Complex [{Mo6I8}Cl6].

Photoactive transition metal compounds that are prone to reversible redox reactions are important for myriad applications, including catalysis, optoelectronics, and sensing. This article describes chemical and electrochemical methods to prepare cluster complex (Bu4N)[{Mo6I8}Cl6], a rare example of a 23 e- cluster complex within the family of octahedral clusters of Mo, W, and Re. The low temperature and room temperature crystal structures; electronic structure; and the magnetic, optical, and electrochemical properties of this complex are described.

Local A-Site Layering in Rare-Earth Orthochromite Perovskites by Solution Synthesis.

Cation size effects were examined in the mixed A-site perovskites La0.5 Sm0.5 CrO3 and La0.5 Tb0.5 CrO3 prepared through both hydrothermal and solid-state methods. Atomically resolved electron energy loss spectroscopy (EELS) in the transmission electron microscope shows that while the La and Sm cations are randomly distributed, increased cation-radius variance in La0.5 Tb0.5 CrO3 results in regions of localised La and Tb layers, an atomic arrangement exclusive to the hydrothermally prepared material. Solid-state preparation gives lower homogeneity resulting in separate nanoscale regions rich in La3+ and Tb3+ . The A-site layering in hydrothermal La0.5 Tb0.5 CrO3 is randomised upon annealing at high temperature, resulting in magnetic behaviour that is dependent on synthesis route.

Exchange of Coordinated Solvent During Crystallization of a Metal-Organic Framework Observed by In Situ High-Energy X-ray Diffraction.

Using time-resolved monochromatic high energy X-ray diffraction, we present an in situ study of the solvothermal crystallisation of a new MOF [Yb2(BDC)3(DMF)2]⋅H2O (BDC=benzene-1,4-dicarboxylate and DMF=N,N-dimethylformamide) under solvothermal conditions, from mixed water/DMF solvent. Analysis of high resolution powder patterns obtained reveals an evolution of lattice parameters and electron density during the crystallisation process and Rietveld analysis shows that this is due to a gradual topochemical replacement of coordinated solvent molecules. The water initially coordinated to Yb(3+) is replaced by DMF as the reaction progresses.

In†Situ Observation of Successive Crystallizations and Metastable Intermediates in the Formation of Metal-Organic Frameworks.

Understanding the driving forces controlling crystallization is essential for the efficient synthesis and design of new materials, particularly metal-organic frameworks (MOFs), where mild solvothermal synthesis often allows access to various phases from the same reagents. Using high-energy in situ synchrotron X-ray powder diffraction, we monitor the crystallization of lithium tartrate MOFs, observing the successive crystallization and dissolution of three competing phases in one reaction. By determining rate constants and activation energies, we fully quantify the reaction energy landscape, gaining important predictive power for the choice of reaction conditions. Different reaction rates are explained by the structural relationships between the products and the reactants; larger changes in conformation result in higher activation energies. The methods we demonstrate can easily be applied to other materials, opening the door to a greater understanding of crystallization in general.

An NMR crystallography study of the hemihydrate of 2', 3'-O-isopropylidineguanosine.

An NMR crystallography study of the hemihydrate of 2', 3'-O-isopropylidineguanosine (Gace) is presented, together with powder X-ray diffraction and thermogravimetric analysis. (1)H double-quantum and (14)N-(1)H HMQC spectra recorded at 850MHz and 75kHz MAS (using a JEOL 1mm probe) are presented together with a (1)H-(13)C refocused INEPT spectrum recorded at 500MHz and 12.5kHz MAS using eDUMBO-122(1)H homonuclear decoupling. NMR chemical shieldings are calculated using the GIPAW (gauge-including projector augmented wave) method; good two-dimensional agreement between calculation and experiment is observed for (13)C and (1)H chemical shifts for directly bonded CH and CH3 peaks. There are two Gace molecules in the asymmetric unit cell: differences in specific (1)H chemical shifts are rationalised in terms of the strength of CH-π and intermolecular hydrogen bonding interactions.