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Open Access
Abstract: Crystals of metal hexachlorides Cs2MCl6 (M = Hf or Zr) have recently emerged as promising materials for scintillation applications due to their excellent energy resolution. In this work, we investigated the crystal structure and scintillation properties of Cs2HfCl6 and Cs2ZrCl6 crystals in the broad temperature range from 9 to 300 K. X-ray diffraction data confirmed the same cubic structure (space group Fm3m) for Cs2HfCl6 and Cs2ZrCl6 over the entire examined temperature range. The room temperature scintillation light yield of Cs2HfCl6 excited with a 137Cs γ-source is measured to be 24[thin space (1/6-em)]800 photons per MeV, while Cs2ZrCl6 exhibits 33[thin space (1/6-em)]900 photons per MeV resulting in energy resolutions of 5.3% and 4.5%, respectively. The alpha-to-beta ratio determined at room temperature for 5.5 MeV α-particles from an 241Am source is equal to 0.39 for Cs2HfCl6 and 0.35 for Cs2ZrCl6. The measurements of scintillation decay curves revealed complex kinetics due to delayed recombination processes. A tangible enhancement of the scintillation yield with heating is observed in the 125–150 K range. This effect is a manifestation of negative thermal quenching explained by thermal activation of trapped carriers. A model of the emission centre is proposed that consistently explains the observed changes of emission intensity with temperature in the crystals under study.
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Apr 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[22410]
Abstract: Metal–organic frameworks (MOFs) can serve as precursors for new nanomaterials via thermal decomposition. Such MOF-derived nanomaterials (MDNs) are often comprised of metal and/or metal oxide particles embedded on porous carbon. The morphology of MDNs is similar to that of the precursor MOF, and improved stability and catalytic properties have been demonstrated. However, the pathway from MOF to MDN is only well understood for a few systems, and in situ studies are needed to elucidate the full phase behaviour and time/temperature dependency. In this work, we follow the MOF-to-MDN transformation in situ by using three complementary techniques: X-ray absorption spectroscopy (XAS), powder X-ray diffraction (PXRD), and X-ray total scattering/pair distribution function (TS/PDF) analysis. The thermal decomposition of HKUST-1, i.e. the archetypical MOF Cu3(btc = 1,3,5-benzenetricarboxylate)2, is followed from room temperature to 500 °C by applying different heating ramps. Real space correlations are followed by PDF and extended X-ray absorption fine structure (EXAFS) analysis, and quantitative phase fractions are obtained by refinement of PXRD and PDF data, and by linear combination analysis (LCA) of X-ray absorption near edge Structure (XANES) data. We find that HKUST-1 decomposes at 300–325 °C into copper(I) oxide and metallic copper. Above 350–470 °C, metal particles remain as the only copper species. There is an overall good agreement between all three techniques with respect to the phase evolution, and the study paves the road towards rational synthesis of a Cu2O/Cu/carbon material with the desired metal/metal oxide composition. More importantly, our investigations serve as a benchmark study demonstrating that this methodology is generally applicable for studying the thermal decomposition of MOFs.
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Apr 2022
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[20570]
Abstract: Complexation of Fe[ClO4]2·6H2O by 1 equiv. 2,6-bis((4S)-4-phenyl-4,5-dihydrooxazol-2-yl)pyridine ((S)-L1Ph) and 2,6-bis((4R)-4-phenyl-4,5-dihydrothiazol-2-yl)pyridine ((R)-L2Ph) cleanly affords [Fe((S)-L1Ph)((R)-L2Ph)][ClO4]2; [Fe((R)-L1iPr)((S)-L2iPr)][ClO4]2 (L1iPr = 2,6-bis(4-isopropyl-4,5-dihydrooxazol-2-yl)pyridine; L2iPr = 2,6-bis(4-isopropyl-4,5-dihydrothiazol-2-yl)pyridine) was prepared by a similar route. The compounds exhibit thermal spin-crossover in solution, at temperatures midway between the corresponding [Fe((R)-L1R)((S)-L1R)][ClO4]2 and [Fe((R)-L2R)((S)-L2R)][ClO4]2 (R = Ph or iPr) species. The spin states of [Fe(LR)(bimpy)][ClO4]2 and [Fe(LR)(bpp)][ClO4]2 (LR = L1R or L2R; bimpy = 2,6-bis(1H-benzimidazol-2-yl)pyridine; bpp = 2,6-di(pyrazol-1-yl)pyridine) are also reported, with most examples exhibiting gradual spin-crossover in solution and the solid state. Although some products undergo partial ligand exchange in solution by 1H NMR, their solution T½ values appear unaffected by this and correlate well with their spin state energies from gas phase DFT calculations. The high-spin state of [Fe(L2R)(bpp)]2+ is more stabilised than expected, compared to the other [Fe(LR)L]2+ complexes studied (L = bimpy, bpp or terpy). That is explained by an interplay between the relative σ-basicities and π-acidities of the two ligands in each molecule. The steric influence of their phenyl or isopropyl ‘R’ substituents stabilises the heteroleptic complexes by up to 5 kcal mol−1, compared to analogues lacking these groups.
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Feb 2022
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[25166]
Abstract: KBiNb2O7 was prepared from RbBiNb2O7 by a sequence of cation exchange reactions which first convert RbBiNb2O7 to LiBiNb2O7, before KBiNb2O7 is formed by a further K-for-Li cation exchange. A combination of neutron, synchrotron X-ray and electron diffraction data reveal that KBiNb2O7 adopts a polar, layered, perovskite structure (space group A11m) in which the BiNb2O7 layers are stacked in a (0, ½, z) arrangement, with the K+ cations located in half of the available 10-coordinate interlayer cation sites. The inversion symmetry of the phase is broken by a large displacement of the Bi3+ cations parallel to the y-axis. HAADF-STEM images reveal that KBiNb2O7 exhibits frequent stacking faults which convert the (0, ½, z) layer stacking to (½, 0, z) stacking and vice versa, essentially switching the x- and y-axes of the material. By fitting the complex diffraction peak shape of the SXRD data collected from KBiNb2O7 it is estimated that each layer has approximately a ~9% chance of being defective - a high level which is attributed to the lack of cooperative NbO6 tilting in the material, which limits the lattice strain associated with each fault.
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Jan 2022
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[18786]
Abstract: Solid state compounds which exhibit non-centrosymmetric crystal structures are of great interest due to the physical properties they can exhibit. The ‘hybrid improper’ mechanism - in which two non-polar distortion modes couple to, and stabilize, a further polar distortion mode, yielding an acentric crystal structure - offers opportunities to prepare a range of novel non-centrosymmetric solids, but examples of compounds exhibiting acentric crystal structures stabilized by this mechanism are still relatively rare. Here we describe a series of bismuth-containing layered perovskite oxide phases, RbBiNb2O7, LiBiNb2O7 and NaBiNb2O7, which have structural frameworks compatible with hybrid-improper ferroelectricity, but also contain Bi3+ cations which are often observed to stabilize acentric crystal structures due to their 6s2 electronic configurations. Neutron powder diffraction analysis reveals that RbBiNb2O7 and LiBiNb2O7 adopt polar crystal structures (space groups I2cm and B2cm respectively), compatible with stabilization by a trilinear coupling of non-polar and polar modes. The Bi3+ cations present are observed to enhance the magnitude of the polar distortions of these phases, but are not the primary driver for the acentric structure, as evidenced by the observation that replacing the Bi3+ cations with Nd3+ cations does not change the structural symmetry of the compounds. In contrast the non-centrosymmetric, but non-polar structure of NaBiNb2O7 (space group P212121) differs significantly from the centrosymmetric structure of NaNdNb2O7, which is attributed to a second-order Jahn-Teller distortion associated with the presence of the Bi3+ cations.
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Oct 2021
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Open Access
Abstract: Luminescence probes that facilitate multimodal non-contact measurements of temperature are of particular interest due to the possibility of cross-referencing results across different readout techniques. This intrinsic referencing is an essential addition that enhances accuracy and reliability of the technique. A further enhancement of sensor performance can be achieved by using two luminescent ions acting as independent emitters, thereby adding in-built redundancy to non-contact temperature sensing, using a single readout technique. In this study we combine both approaches by engineering a material with two luminescent ions that can be independently probed through different readout modes of non-contact temperature sensing. The approach was tested using Al2O3 co-doped with Cr3+ and Mn4+, exhibiting sharp emission lines due to 2E → 4A2 transitions. The temperature sensing performance was examined by measuring three characteristics: temperature-induced changes of the intensity ratio of the emission lines, their spectral position, and the luminescence decay time constant. The processes responsible for the changes with temperature of the measured luminescence characteristics are discussed in terms of relevant models. By comparing temperature resolutions achievable by different modes of temperature sensing it is established that in Al2O3-Cr,Mn spectroscopic methods provide the best measurement accuracy over a broad temperature range. A temperature resolution better than ±2.8 K can be achieved by monitoring the luminescence intensity ratio (40–145 K) and the spectral shift of the R-line of Mn4+ (145–300 K range).
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Sep 2021
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[22240]
Open Access
Abstract: Amido-zincates containing hydrides are underexplored yet potentially useful complexes. Attempts to access this type of zincate through combining amido-organo zincates and pinacolborane (HBPin) via a Zn-C / H-B exchange led instead to preferential formation of amide-BPin and/or [amide-BPin(Y)]- (Y = Ph, amide, H), when the amide is hexamethyldisilazide or 2,2,6,6-tetramethylpiperidide and the hydrocarbyl group was phenyl or ethyl. In contrast, the use of a dipyridylamide (dpa) based arylzincate led to Zn-C/HBPin metathesis being the major outcome. Independent synthesis and full characterisation of two (donor)Li[(dpa)ZnPh2] (donor = 3 x THF or 1 x PMDETA) complexes, 1 and 3, respectively, enabled reactivity studies confirming these species display zincate type reactivity (by comparison to the reactivity of the neutral complex Me-NdpaZnPh2, 4). This included 1 performing the rapid deprotonation of a terminal alkyne and also phenyl transfer to α,α,α-trifluoroacetophenone in contrast to neutral complex 4. Complex 1 reacted with one equivalent of HBPin to give predominantly PhBPin (90%) and a lithium amidophenylzincate containing a hydride unit, complex 7, as the second major product. Complex 7 transfers hydride to an electrophile preferentially over phenyl, indicating it can react as a hydridozincate. Attempts to react 1 with > 1 equivalent of HBPin or with catecholborane led to more complex outcomes, which included significant borane and dpaZn substituent scrambling, two examples of which were crystallographically characterised. While this work provides proof of principle for Zn-C/H-BPin exchange as a route to form an amido-zincate containing a hydride, amido-organozincates that undergo more selective Zn-C/H-BPin exchange still are required.
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Sep 2021
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I11-High Resolution Powder Diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[18786, 20375]
Open Access
Abstract: Intercalation of lithium and ammonia into the layered semiconductor Bi2Se3 proceeds via a hyperextended (by >60%) ammonia-rich intercalate, to eventually produce a layered compound with lithium amide intercalated between the bismuth selenide layers which offers scope for further chemical manipulation.
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Aug 2021
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[20570]
Abstract: The synthesis of six 2,6-di(pyrazol-1-yl)pyridine derivatives bearing dithiolane or carboxylic acid tether groups is described: [2,6-di(pyrazol-1-yl)pyrid-4-yl]methyl (R)-lipoate (L1), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]ethyl (R)-lipoate (L2), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxy]ethyl (R)-lipoate (L3), N-([2,6-di(pyrazol-1-yl)pyrid-4-ylsulfanyl]-2-aminoethyl (R)-lipoamide (L4), 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]acetic acid (L5) and 2-[(2,6-di(pyrazol-1-yl)pyridine)-4-carboxamido]propionic acid (L6). The iron(II) perchlorate complexes of all the new ligands exhibit gradual thermal spin-crossover (SCO) in the solid state above room temperature, except L4 whose complex remains predominantly high-spin. Crystalline [Fe(L6)2][ClO4]2·2MeCN contains three unique cation sites which alternate within hydrogen-bonded chains, and undergo gradual SCO at different temperatures upon warming. The SCO midpoint temperature (T1/2) of the complexes in CD3CN solution ranges between 208–274 K, depending on the functional group linking the tether groups to the pyridyl ring. This could be useful for predicting how these complexes might behave when deposited on gold or silica surfaces.
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May 2021
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I11-High Resolution Powder Diffraction
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Abstract: Recently, broad-band white-light-emitting using Eu2+, Ce3+, or Bi3+ in multi-sites of a single-phase phosphor have drawn extensive attention due to their potential to realize high-quality indoor lighting. This work reports a novel oxide Ca7Mg2Ga6O18 (CMG) possessing a complex crystal structure in the space group F432. The Rietveld refinements of high-resolution synchrotron X-ray diffraction data were performed to determine the accurate atomic positions and occupancy factors, giving a reasonable composition Ca7Mg1.91(4)Ga6.09(4)O18. Due to the multiple sites of Ca2+, which are suitable for doping of Bi3+ activators, CMG is a promising host to achieve broad-band white-light emission. Detailed structural and spectroscopic analyses revealed that the Bi3+-activator show multiple and site-selective occupancy, which is the origin of the red-shifts in both broad-band excitation and emission spectra upon increasing the Bi3+ content. A series of Bi3+ and Eu3+ codoped phosphors with tunable blue-pink-red emission were prepared due to the Bi3+-to-Eu3+ energy transfer. Distinctive thermal behaviors of Bi3+ and Eu3+ emissions make CMG:Bi3+,Eu3+a candidate to the optical thermometer.
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Apr 2021
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