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123 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3, 4, 5, 6, 7, 8 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I11-High Resolution Powder Diffraction	Sn6SiO8, a tin(II) silicate with a zinc blende related structure and high thermal stability Daniel S. Parsons , Savvaki N. Savva , Wai Chi Tang , Andrew Ingram , Joseph A. Hriljac Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02615 Diamond Proposal Number(s): [12092] Show Abstract ▼ Abstract: The crystal structure of a novel cubic tin(II) silicate, Sn6SiO8 (space group F4̅3m, a = 10.40708(2) Å, and Z = 4), synthesized by microwave-assisted hydrothermal synthesis has been solved by Rietveld refinement of the powder X-ray diffraction (PXRD) data. The structure, analogous to zinc blende, comprises a face-centered-cubic array of [Sn6O8]4– anions, with Si4+ occupying half of the tetrahedral holes. The tin(II) silicate has been further characterized by variable-temperature PXRD, demonstrating stability of the structure and resistance to SnII oxidation up to ∼600 °C, when the compound begins to thermally decompose.	Dec 2019
I11-High Resolution Powder Diffraction	Average and local structure of apatite-type germanates and implications for oxide ion conductivity Mathew S. Chambers , Philip A. Chater , Ivana Radosavljevic Evans , John S. O. Evans Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02544 Diamond Proposal Number(s): [14188] Show Abstract ▼ Abstract: Materials with the apatite structure have a range of important applications in which their function is influenced by details of their local structure. Here, we describe an average and local structural study to probe the origins of high-temperature oxide ion mobility in La10(GeO4)6O3 and La8Bi2(GeO4)6O3 oxygen-excess materials, using the low-conductivity interstitial oxide-free La8Sr2(GeO4)6O2 as a benchmark. For La10 and La8Bi2, we locate the interstitial oxygen, Oint, responsible for conductivity by Rietveld refinement and relate the P63/m to P1̅ phase transitions on cooling to oxygen ordering. Local structural studies using neutron total scattering reveal that well-ordered GeO5 square pyramidal groups form in the structure at low temperature, but that Oint becomes significantly more disordered in the high-conductivity, high-temperature structures, with a transition to more trigonal-bipyramid-like average geometry. We relate the higher conductivity of Bi materials to the presence of several Oint sites of similar energy in the structure, which correlates with its less-distorted low-temperature average structure.	Oct 2019
I11-High Resolution Powder Diffraction	Exsolution of SrO during the topochemical conversion of LaSr3CoRuO8 to the oxyhydride LaSr3CoRuO4H4 Lun Jin , Maria Batuk , Franziska K. K. Kirschner , Franz Lang , Stephen J. Blundell , Joke Hadermann , Michael A. Hayward Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02552 Diamond Proposal Number(s): [13284] Show Abstract ▼ Abstract: Reaction of the n = 1 Ruddlesden–Popper oxide LaSr3CoRuO8 with CaH2 yields the oxyhydride phase LaSr3CoRuO4H4 via a topochemical anion exchange. Close inspection of the X-ray and neutron powder diffraction data in combination with HAADF-STEM images reveals that the nanoparticles of SrO are exsolved from the system during the reaction, with the change in cation stoichiometry accommodated by the inclusion of n > 1 (Co/Ru)nOn+1H2n “perovskite” layers into the Ruddlesden–Popper stacking sequence. This novel pseudotopochemical process offers a new route for the formation of n > 1 Ruddlesden–Popper structured materials. Magnetization data are consistent with a LaSr3Co+Ru2+O4H4 (Co+, d8, S = 1; Ru2+, d6, S = 0) oxidation/spin state combination. Neutron diffraction and μ+SR data show no evidence for long-range magnetic order down to 2 K, suggesting the diamagnetic Ru2+ centers impede the Co–Co magnetic-exchange interactions.	Oct 2019
I19-Small Molecule Single Crystal Diffraction	Macropolyhedral nickelaboranes from the metal-assisted fusion of KB9H14 Michael G. S. Londesborough , Ramón Macías , John D. Kennedy , William Clegg , Jonathan Bould Inorganic Chemistry 58, 13258-13267 DOI: 10.1021/acs.inorgchem.9b02116 Diamond Proposal Number(s): [16117] Show Abstract ▼ Abstract: The reaction of K[arachno-B9H14] with [NiCl2(dppe)] produces four new 19-vertex macropolyhedral metallaboranes that result from borane cluster fusion: [9′-(dppe)-9′-Ni-anti-B18H20] (1) and isomeric [11′-(dppe)-11′-Ni-syn-B18H20] (2), together with the chlorine-substituted derivative of 1, [5′-Cl-9′-(dppe)-9′-Ni-anti-B18H19] (3), and the 18-vertex cluster compound [7′-(dppe)-7′-anti-NiB17H21] (4). Two closo 10-vertex single-cluster species, [1-(dppe)-1-closo-NiB9H7Cl2] (5) and [1-(dppe)-1-closo-NiB9H7Cl(OH)] (6), were also isolated from the reaction. The production of the metalated syn-octadecaborane isomer 2 from the fusion of two arachno-nonaborate clusters is the first such case to be observed; in all other reported cases fusion has resulted in products with the anti-octadecaboranyl bis-nido configuration.	Sep 2019
I11-High Resolution Powder Diffraction	Iodine adsorption in a redox-active metal–organic framework: electrical conductivity induced by host−guest charge-transfer Xinran Zhang , Ivan Da Silva , Rodrigo Fazzi , Alena M. Sheveleva , Xue Han , Ben F. Spencer , Sergey A. Sapchenko , Floriana Tuna , Eric J. L. Mcinnes , Ming Li , Sihai Yang , Martin Schroder Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b02176 Diamond Proposal Number(s): [21079] Show Abstract ▼ Abstract: We report a comparative study of the binding of I2 (iodine) in a pair of redox-active metal–organic framework (MOF) materials, MFM-300(VIII) and its oxidized, deprotonated analogue, MFM-300(VIV). Adsorption of I2 in MFM-300(VIII) triggers a host-to-guest charge-transfer, accompanied by a partial (∼30%) oxidation of the VIII centers in the host framework and formation of I3– species residing in the MOF channels. Importantly, this charge-transfer induces a significant enhancement in the electrical conductivity (Δσ = 700000) of I2@MFM-300(VIII/IV) in comparison to MFM-300(VIII). In contrast, no host–guest charge-transfer or apparent change in the conductivity was observed upon adsorption of I2 in MFM-300(VIV). High-resolution synchrotron X-ray diffraction of I2@MFM-300(VIII/IV) confirms the first example of self-aggregation of adsorbed iodine species (I2 and I3–) into infinite helical chains within a MOF.	Sep 2019
I11-High Resolution Powder Diffraction	Increasing alkyl chain length in a series of layered metal–organic frameworks aids ultrasonic exfoliation to form nanosheets David J. Ashworth , Thomas M. Roseveare , Andreas Schneemann , Max Flint , Irene Dominguez Bernáldes , Pia Vervoorts , Roland A. Fischer , Lee Brammer , Jonathan A. Foster Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b01128 Show Abstract ▼ Abstract: Metal–organic framework nanosheets (MONs) are attracting increasing attention as a diverse class of two-dimensional materials derived from metal–organic frameworks (MOFs). The principles behind the design of layered MOFs that can readily be exfoliated to form nanosheets, however, remain poorly understood. Here we systematically investigate an isoreticular series of layered MOFs functionalized with alkoxy substituents in order to understand the effect of substituent alkyl chain length on the structure and properties of the resulting nanosheets. A series of 2,5-alkoxybenzene-1,4-dicarboxylate ligands (O2CC6H2(OR)2CO2, R = methyl–pentyl, 1–5, respectively) was used to synthesize copper paddle-wheel MOFs. Rietveld and Pawley fitting of powder diffraction patterns for compounds Cu(3–5)(DMF) showed they adopt an isoreticular series with two-dimensional connectivity in which the interlayer distance increases from 8.68 Å (R = propyl) to 10.03 Å (R = pentyl). Adsorption of CO2 by the MOFs was found to increase from 27.2 to 40.2 cm3 g–1 with increasing chain length, which we attribute to the increasing accessible volume associated with increasing unit-cell volume. Ultrasound was used to exfoliate the layered MOFs to form MONs, with shorter alkyl chains resulting in higher concentrations of exfoliated material in suspension. The average height of MONs was investigated by AFM and found to decrease from 35 ± 26 to 20 ± 12 nm with increasing chain length, with the thinnest MONs observed being only 5 nm, corresponding to five framework layers. These results indicate that careful choice of ligand functionalities can be used to tune nanosheet structure and properties, enabling optimization for a variety of applications.	Aug 2019
I18-Microfocus Spectroscopy	Synchrotron radiation X-ray fluorescence elemental mapping in healthy versus malignant prostate tissues provides new insights into the glucose-stimulated zinc trafficking in the prostate as discovered by MRI Veronica Clavijo Jordan , Alia Al-ebraheem , Kalotina Geraki , Eric Dao , Andre F. Martins , Sara Chirayil , Michael Farquharson , A. Dean Sherry Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b01132 Diamond Proposal Number(s): [14747] Show Abstract ▼ Abstract: Prostatic zinc content is a known biomarker for discriminating normal healthy tissue from benign prostatic hyperplasia (BPH) and prostate cancer (PCa). Given that zinc content is not readily measured without a tissue biopsy, we have been exploring noninvasive imaging methods to detect these diagnostic differences using a zinc-responsive MRI contrast agent. During imaging studies in mice, we observed that a bolus of glucose stimulates secretion of zinc from the prostate of fasted mice. This discovery allowed the use of a Gd-based zinc sensor to detect differential zinc secretion in regions of healthy versus malignant prostate tissue in a transgenic adenocarcinoma mouse model of PCa. Here, we used a zinc-responsive MRI agent to detect zinc release across the prostate during development of malignancy and confirm the loss of total tissue zinc by synchrotron radiation X-ray fluorescence (μSR-XRF). Quantitative μSR-XRF results show that the lateral lobe of the mouse prostate uniquely accumulates high concentrations of zinc, 1.06 ± 0.08 mM, and that the known loss of zinc content in the prostate is only observed in the lateral lobe during development of PCa. Additionally, we confirm that lesions identified by a loss of zinc secretion indeed represent malignant neoplasia and that the relative zinc concentration in the lesion is reduced to 0.370 ± 0.001 mM. The μSR-XRF data also provided insights into the mechanism of zinc secretion by showing that glucose promotes movement of zinc pools (∼1 mM) from the glandular lumen of the lateral lobe of the mouse prostate into the stromal/smooth muscle surrounding the glands. Co-localization of zinc and gadolinium in the stromal/smooth muscle areas as detected by μSR-XRF confirm that glucose initiates secretion of zinc from intracellular compartments into the extracellular spaces of the gland where it binds to the Gd-based agent and albumin promoting MR image enhancement.	Jul 2019
I15-Extreme Conditions	High-pressure study of the elpasolite perovskite La2NiMnO6 Christopher J. Ridley , Dominik Daisenberger , Craig W. Wilson , Gavin B. G. Stenning , Gopinathan Sankar , Kevin S. Knight , Matthew Tucker , Ronald I. Smith , Craig L. Bull Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b00404 Diamond Proposal Number(s): [11828] Show Abstract ▼ Abstract: Here we report a high-pressure investigation into the structural and magnetic properties of the double perovskite La2NiMnO6 using neutron scattering over a temperature range of 4.2–300 K at ambient pressure and over a temperature range of 120–1177 K up to a maximum pressure of 6.6 GPa. X-ray diffraction was also used up to a maximum pressure of 64 GPa, over a temperature range of 300–720 K. The sample was found to exist in a mixed rhombohedral/monoclinic symmetry at ambient conditions, the balance of which was found to be strongly temperature- and pressure-dependent. Alternating current magnetometry and X-ray absorption near-edge structure measurements were made at ambient pressure to characterize the sample, suggesting that the transition-metal sites exist in a mixed Ni3+/Mn3+ and Ni2+/Mn4+ state at ambient temperature and pressure. Analysis of the magnetic properties of the sample shows that the Curie temperature can be enhanced by ∼12 K with 2 GPa applied pressure, but it is highly stable at pressures beyond this. We report a pressure–volume–temperature equation of state for this material over this combined temperature and pressure range, with an ambient temperature bulk modulus of ∼179(8) GPa. The previously reported transition from monoclinic to rhombohedral symmetry upon heating to 700 K is seen to be encouraged with applied pressure, transforming fully by ∼1.5 GPa. Raman spectroscopy data were collected up to ∼8 GPa and show no clear changes or discontinuities over the reported phase transition to rhombohedral symmetry or any indication of further changes over the range considered. The ambient-pressure Grüneisen parameter γth was determined to be γth = 2.6 with a Debye temperature of 677 K. The individual modal parameters γj at ambient temperature were also determined from the high-pressure Raman data.	Jun 2019
I15-1-X-ray Pair Distribution Function (XPDF)	Local structure and influence of Sb substitution on the structure–transport properties in AgBiSe2 Tim Bernges , Jan Peilstöcker , Moniak Dutta , Saneyuki Ohno , Kanishka Biswas , Wolfgang Zeier Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b00874 Diamond Proposal Number(s): [21273] Show Abstract ▼ Abstract: Owing to their intrinsically low thermal conductivity and chemical diversity, materials within the I–V–VI2 family, and especially AgBiSe2, have recently attracted interest as promising thermoelectric materials. However, further investigations are needed in order to develop a more fundamental understanding of the origin of the low thermal conductivity in AgBiSe2, to evaluate possible stereochemical activity of the 6s2 lone pair of Bi3+, and to further elaborate on chemical design approaches for influencing the occurring phase transitions. In this work, a combination of temperature-dependent X-ray diffraction, Rietveld refinements of laboratory X-ray diffraction data, and pair distribution function analyses of synchrotron X-ray diffraction data is used to tackle the influence of Sb substitution within AgBi1–xSbxSe2 (0 ⩽ x ⩽ 0.15) on the phase transitions, local distortions, and off-centering of the structure. This work shows that, similar to other lone-pair-containing materials, local off-centering and distortions can be found in AgBiSe2. Furthermore, electronic and thermal transport measurements, in combination with the modeling of point-defect scattering, highlight the importance of structural characterizations toward understanding changes induced by elemental substitutions. This work provides new insights into the structure–transport correlations of the thermoelectric AgBiSe2.	Jun 2019
I11-High Resolution Powder Diffraction	CaMn0.5Ir0.5O2.5: an anion-deficient perovskite oxide containing Ir3+ Jacob E. Page , Michael A. Hayward Inorganic Chemistry DOI: 10.1021/acs.inorgchem.9b01219 Diamond Proposal Number(s): [13284] Show Abstract ▼ Abstract: Reaction between CaMn0.5Ir0.5O3 and NaH, either through solid-solid contact or via a gas mediated reaction process, yields the topochemically reduced phase CaMn0.5Ir0.5O2.5 in which Mn3+ and Ir3+ cations are located within a partially anion-vacancy disordered lattice. Magnetization data from CaMn0.5Ir0.5O2.5 can be fit by the Curie–Weiss law to yield C = 1.586 cm3 K mol–1 and θ = −86.9 K, consistent with a combination of S = 2, Mn3+ and S = 0, Ir3+. On cooling below T ∼ 110 K, the system undergoes a transition to a spin-glass state, consistent with the observed Mn/Ir cation disorder and frustration between Mn-O-Mn and Mn-O-Ir-O-Mn magnetic couplings. The degree of reduction and the observed anion-vacancy disorder are discussed on the basis of the d-orbital filling of the transition-metal cations.	Jun 2019

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