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129 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	Chemical and electrochemical lithiation of van der Waals oxytelluride V2Te2O Nicola D. Kelly , Heather Grievson , Katherine M. Steele , Ivan Da Silva , Simon J. Clarke Dalton Transactions 9 DOI: 10.1039/D5DT00159E Diamond Proposal Number(s): [32893] Open Access Show Abstract ▼ Abstract: Reversible lithium intercalation into the van der Waals phase V2Te2O, forming new phases LixV2Te2O with x approaching 2, is reported using both chemical and electrochemical methods. The progress of each reaction was followed using powder X-ray diffraction and the crystal structure of the intercalated phase with x = 1, LiV2Te2O, was refined using powder neutron diffraction. The intercalated Li ions occupy vacant pseudo-octahedral sites and the unit cell expands on reduction with no change in symmetry. The lithium ions can be removed chemically or electrochemically, making this the first known oxytelluride to undergo reversible lithium intercalation.	Feb 2025
I19-Small Molecule Single Crystal Diffraction	Radical-cation salts of BEDT-TTF with tris-coordinated racemic dysprosium(iii) and terbium(iii) anions Emily Howarth , Jordan Lopez , Joseph O. Ogar , Toby J. Blundell , Hiroki Akutsu , Yasuhiro Nakazawa , Shusaku Imajo , Yoshihiko Ihara , Simon J. Coles , Peter N. Horton , Jeppe Christensen , Lee Martin Dalton Transactions 104 DOI: 10.1039/D4DT03484H Open Access Show Abstract ▼ Abstract: This paper reports the synthesis, crystal structures and conducting properties of the first BEDT-TTF radical-cation salts with D3 symmetry tris-coordinated racemic lanthanide(III) anions. It is also the first crystallographic determination of the nine-coordinate tris(chelidonato)terbate and tris(chelidonato)dysprosate anions (chelidonic acid = clo = 4-oxo-4H-pyran-2,6-dicarboxylic acid). Salt α-(BEDT-TTF)5M(chelidonato)3·EtOH·2H2O is semimetallic for M = Tb, and semiconducting for M = Dy. These conducting properties are consistent with the band structure for both salts.	Jan 2025
I19-Small Molecule Single Crystal Diffraction	Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes Tajrian Chowdhury , Claire Wilson , Joy H. Farnaby Dalton Transactions 336 DOI: 10.1039/D4DT01382D Diamond Proposal Number(s): [31778] Open Access Show Abstract ▼ Abstract: Synthesis and reactivity with carbon dioxide (CO2) of divalent samarium in the bis-tris(pyrazolyl)borate ligand environment has been reported. In addition, CO2 activation and functionalisation by lanthanide silylamides in the bis-tris(pyrazolyl)borate ligand environment was demonstrated. Reduction of the Sm(III) precursor [Sm(Tp)2(OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf = triflate) with KC8 yielded the insoluble Sm(II) multi-metallic coordination polymer [{Sm(Tp)2}n] 1-Sm. Addition of 1,2-dimethoxyethane (DME) to 1-Sm enabled isolation of the monomeric complex [Sm(Tp)2(DME)] 1-Sm(DME). Complex 1-Sm(DME) reduced CO2 to yield the oxalate-bridged dimeric Sm(III) complex [{Sm(Tp)2}2(μ-η2:η2-O2CCO2)] 2-Sm. The reactions of heteroleptic Ln(III) silylamide complexes [Ln(Tp)2(N′′)] (Ln = Y, Sm; N′′ = N(SiMe3)2) with CO2 yielded monomeric Ln(III) silyloxides [Ln(Tp)2(OSiMe3)] 3-Ln and trimethylsilyl isocyanate (O[double bond, length as m-dash]C[double bond, length as m-dash]NSiMe3). Complexes 3-Ln are the first crystallographically characterised examples of Ln(III)–OSiMe3 bonds accessed via CO2 activation and functionalisation. Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.	Jun 2024
I15-1-X-ray Pair Distribution Function (XPDF)	Loading and thermal behaviour of ZIF-8 metal–organic framework-inorganic glass composites Ashleigh M. Chester , Celia Castillo-Blas , Roman Sajzew , Bruno P. Rodrigues , Giulio I. Lampronti , Adam F. Sapnik , Georgina P. Robertson , Matjaž Mazaj , Daniel J. M. Irving , Lothar Wondraczek , David A. Keen , Thomas D. Bennett Dalton Transactions 46 DOI: 10.1039/D4DT00894D Open Access Show Abstract ▼ Abstract: Here we describe the synthesis of a compositional series of metal–organic framework crystalline-inorganic glass composites (MOF-CIGCs) containing ZIF-8 and an inorganic phosphate glass, 20Na2O–10NaCl–70P2O5, to expand the library of host matrices for metal–organic frameworks. By careful selection of the inorganic glass component, a relatively high loading of ZIF-8 (70 wt%) was achieved, which is the active component of the composite. A Zn⋯O–P interfacial bond, previously identified in similar composites/hybrid blends, was suggested by analysis of the total scattering pair distribution function data. Additionally, CO2 and N2 sorption and variable-temperature PXRD experiments were performed to assess the composites’ properties.	Jun 2024
	Beyond the coupled distortion model: structural analysis of the single domain cupredoxin AcoP, a green mononuclear copper centre with original features Magali Roger , Philippe Leone , Ninian J. Blackburn , Sam Horrell , Tadeo Moreno Chicano , Frédéric Biaso , Marie-Thérèse Giudici-Orticoni , Luciano A. Abriata , Greg L. Hura , Michael A. Hough , Giuliano Sciara , Marianne Ilbert Dalton Transactions 114 DOI: 10.1039/D3DT03372D Open Access Show Abstract ▼ Abstract: Cupredoxins are widely occurring copper-binding proteins with a typical Greek-key beta barrel fold. They are generally described as electron carriers that rely on a T1 copper centre coordinated by four ligands provided by the folded polypeptide. The discovery of novel cupredoxins demonstrates the high diversity of this family, with variations in terms of copper-binding ligands, copper centre geometry, redox potential, as well as biological function. AcoP is a periplasmic cupredoxin belonging to the iron respiratory chain of the acidophilic bacterium Acidithiobacillus ferrooxidans. AcoP presents original features, including high resistance to acidic pH and a constrained green-type copper centre of high redox potential. To understand the unique properties of AcoP, we undertook structural and biophysical characterization of wild-type AcoP and of two Cu-ligand mutants (H166A and M171A). The crystallographic structures, including native reduced AcoP at 1.65 Å resolution, unveil a typical cupredoxin fold. The presence of extended loops, never observed in previously characterized cupredoxins, might account for the interaction of AcoP with physiological partners. The Cu-ligand distances, determined by both X-ray diffraction and EXAFS, show that the AcoP metal centre seems to present both T1 and T1.5 features, in turn suggesting that AcoP might not fit well to the coupled distortion model. The crystal structures of two AcoP mutants confirm that the active centre of AcoP is highly constrained. Comparative analysis with other cupredoxins of known structures, suggests that in AcoP the second coordination sphere might be an important determinant of active centre rigidity due to the presence of an extensive hydrogen bond network. Finally, we show that other cupredoxins do not perfectly follow the coupled distortion model as well, raising the suspicion that further alternative models to describe copper centre geometries need to be developed, while the importance of rack-induced contributions should not be underestimated.	Jan 2024
I19-Small Molecule Single Crystal Diffraction	2-(Thienyl)quinoxaline derivatives and their application in Ir(iii) complexes yielding tuneable deep red emitters Sophie A. Fitzgerald , Ellie N. Payce , Peter N. Horton , Simon J. Coles , Simon J. A. Pope Dalton Transactions 2 DOI: 10.1039/D3DT02193A Diamond Proposal Number(s): [31778] Open Access Show Abstract ▼ Abstract: The synthesis and characterisation of eleven different 2-(thienyl)quinoxaline species that incorporate different points of functionality, including at the thiophene or quinoxaline rings, are described. These species display variable fluorescence properties in the visible region (λem = 401–491 nm) depending upon the molecular structures and extent of conjugation. The series of 2-(thienyl)quinoxaline species were then investigated as cyclometalating agents for Ir(III) to yield [Ir(C^N)2(bipy)]PF6 (where C^N = the cyclometalated ligand; bipy = 2,2′-bipyridine). Eight complexes were successfully isolated and fully characterised by an array of spectroscopic and analytical techniques. Two Ir(III) examples were structurally characterised in the solid state using single crystal X-ray diffraction; both structures confirmed the proposed formulations and coordination spheres in each case showing that the thiophene coordinates via a Ir–C bond. The photophysical properties of the complexes revealed that each complex is luminescent under ambient conditions with a range of emission wavelengths observed (665–751 nm) indicating that electronic tuning can be achieved via both the thienyl and quinoxaline moieties.	Oct 2023
I11-High Resolution Powder Diffraction	Structural variation, magnetism and single-source deposition of lanthanide-containing polyoxotitanates Rosa Müller , Olivia Georghiades , Joshua D. Bocarsly , Farheen N. Sayed , Víctor Riesgo-González , Andrew D. Bond , Clare P. Grey , Dominic S. Wright Dalton Transactions 107 DOI: 10.1039/D3DT02553E Diamond Proposal Number(s): [28349] Open Access Show Abstract ▼ Abstract: Heterometal-containing polyoxotitanates (POTs) are much-studied single-source precursors (SSPs) for doped TiO2. In this work the properties of a wide range of lanthanide-containing POTs are studied to assess their potential use as SSPs for Ln–Ti hybrid oxides. The novel cage compounds [{Ti2O(OEt)8}(EtOH·LnCl)]2 (Ln = Sm, Gd, Tb, Dy, Ho, Tm and Yb) are structurally characterised. The magnetic properties of the Ln = Dy and Ho compounds were characterised using SQUID magnetometry—in both cases, there is evidence of significant uniaxial magnetic anisotropy, but magnetic relaxation is fast and therefore no single-molecule magnetic properties are observed. Upon decomposition lanthanide-doped anatase (Ln = La) or titania/LnTi–oxide mixtures are obtained, which show efficient stabilisation of the catalytically active anatase phase up to high temperatures, making the materials of potential interest for applications in photocatalysis.	Sep 2023
B21-High Throughput SAXS	Stretching the chains: the destabilizing impact of Cu 2+ and Zn 2+ ions on K48-linked diubiquitin Vincenzo Mangini , Giulia Grasso , Benny D. Belviso , Michele F. M. Sciacca , Valeria Lanza , Rocco Caliandro , Danilo Milardi Dalton Transactions 22 DOI: 10.1039/D3DT01815F Diamond Proposal Number(s): [21741] Show Abstract ▼ Abstract: Ubiquitin signalling and metal homeostasis play key roles in controlling several physiological cellular activities, including protein trafficking and degradation. While some relationships between these two biochemical pathways have started to surface, our knowledge of their interplay remains limited. Here, we employ a variety of techniques, such as circular dichroism, differential scanning calorimetry, pressure perturbation calorimetry, fluorescence emission, SDS-PAGE, and small-angle X-ray scattering (SAXS) to evaluate the impact of Cu2+ and Zn2+ ions on the structure and stability of K48 linked diubiquitin (K48-Ub2), a simple model for polyubiquitin chains. The SAXS analysis results show that the structure of the metal-free protein is similar to that observed when the protein is bound to the E2 conjugating enzyme, lending support to the idea that the structure of unanchored K48-linked ubiquitin chains is sufficient for identification by conjugating enzymes without the need for an induced fit mechanism. Our results indicate that K48-Ub2 can coordinate up to four metal ions with both copper and zinc ions inducing slight changes to the secondary structure of the protein. However, we noted significant distinctions in their impacts on protein stability and overall architecture. Specifically, Cu2+ ions resulted in a destabilization of the protein structure, which facilitated the formation of dimer aggregates. Next, we observed a shift in the conformational dynamics of K48-Ub2 toward less compact and more flexible states upon metal ion binding, with Zn2+ inducing a more significant effect than Cu2+ ions. Our structural modelling study demonstrates that both metal ions induced perturbations in the K48-Ub2 structure, leading to the separation of the two monomers thus inhibiting interactions with E2 enzymes. In conclusion, the findings from this study enhance our comprehension of the mechanisms underlying Ub chains recognition. Moreover, they strengthen the notion that drug discovery initiatives aimed at targeting metal-mediated disruptions in Ub signaling hold great potential for treating a wide range of diseases that stem from abnormal protein accumulation.	Aug 2023
I19-Small Molecule Single Crystal Diffraction	Quantitative Raman microscopy to describe structural organisation in hollow microcrystals built from silicon catecholate and amines Victor V. Volkov , Toby J. Blundell , Stephen Argent , Carole C. Perry Dalton Transactions DOI: 10.1039/D3DT00856H Diamond Proposal Number(s): [298766] Open Access Show Abstract ▼ Abstract: Macroscopic scale hollow microcrystals are a promising group of materials for gas and liquid uptake as well as sensing. In this contribution we describe the structure of hollow hexagonal cross-section crystals formulated as salts of a silicon catecholate anion and a tetramethylenediamine (TEMED) cation. Using a combination of X-ray single crystal diffraction, Raman spectroscopy and quantum chemistry we explore the structural properties of the hollow microcrystals. With the X-ray structural data as a starting point and assisted with quantum chemistry we compute Raman tensors to fit polarisation sensitive spectral responses and predict the orientation and packing of unit cells in respect to the long and short axis of the synthesised microcrystals. Using these newly developed methods for predicting molecular Raman responses in space with dependence on local orientation, we present the quantitative analysis of experimental Raman images of both hexagonal and tetragonal cross section hollow microcrystals formed from silicon catecholate anions using different amines as counterions. We describe the distributions of chemical components at the surfaces and edges of microcrystals, address the effect of catcholate hydrophobicity on water uptake and discuss possible strategies in chemical and post-assembly modifications to widen the functional properties of this group of environmentally friendly silicon organic framework (SOF) materials.	May 2023
I11-High Resolution Powder Diffraction	Energetics of formation and stability in high pressure steam of barium lanthanide cobaltite double perovskites Aleksandra Mielewczyk-Gryń , Shuhao Yang , Maria Balaguer , Ragnar Strandbakke , Magnus H. Sørby , Iga Szpunar , Agnieszka Witkowska , Sebastian Wachowski , Jose M. Serra , Alexandra Navrotsky , Maria Gazda Dalton Transactions 91 DOI: 10.1039/D2DT03989C Show Abstract ▼ Abstract: This study concerns energetics of formation and the stability in high water partial pressure of BaLnCo2O6−δ, (Ln = La, Pr, Nd, and Gd) (BLnC) and BaGd1−xLaxCo2O6−δ, where x = 0.2, 0.5, and 0.7 (BGLC) double perovskite cobaltites. Those materials are extensively studied due to their potential applications as a positrode in electrochemical devices. Therefore, their stability under such conditions is a key issue. All investigated materials are thermodynamically stable relative to binary oxides and exhibit strongly exothermic enthalpies of formation. Moreover, BaGd0.3La0.7Co2O6−δ and BaGd0.8La0.2Co2O6−δ remain the main perovskite structure up to 3 bars of water vapor at 400 °C. At higher steam pressure, reaching 10 bar at 300 °C, the partial decomposition to constituent oxides and hydroxides was observed. The BGLC compounds exhibit higher negative formation enthalpies in comparison to single-Ln compositions, which does not translate into higher chemical stability under high steam pressures since the BLnC series retained the main perovskite structure at higher temperatures as well as in higher water vapor pressures.	Apr 2023

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