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Instruments / Technical Area	Publication Details	Published
I11-High Resolution Powder Diffraction I19-Small Molecule Single Crystal Diffraction	Structural and electronic effects of X-ray irradiation on prototypical [M(COD)Cl]2 catalysts Nathalie K. Fernando , Andrew B. Cairns , Claire A. Murray , Amber L. Thompson , Joshua L. Dickerson , Elspeth F. Garman , Nayera Ahmed , Laura E. Ratcliff , Anna Regoutz The Journal Of Physical Chemistry A DOI: 10.1021/acs.jpca.1c05759 Diamond Proposal Number(s): [19420, 22705] Show Abstract ▼ Abstract: X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray–matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl]2 and [Rh(COD)Cl]2, exposed to radiation in X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiments. From these complementary techniques, changes to structure, chemical environments, and electronic structure are observed as a function of X-ray exposure, allowing comparisons of stability to be made between the two catalysts. Radiation dose is estimated using recent developments to the RADDOSE-3D software for small molecules and applied to powder XRD and XPS experiments. Further insights into the electronic structure of the catalysts and changes occurring as a result of the irradiation are drawn from density functional theory (DFT). The techniques combined here offer much needed insight into the X-ray-induced effects in transition-metal catalysts and, consequently, their intrinsic stabilities. There is enormous potential to extend the application of these methods to other small molecular systems of scientific or industrial relevance.	Aug 2021
I15-Extreme Conditions	Probing the influence of defects, hydration, and composition on prussian blue analogues with pressure Hanna L. B. Bostroem , Ines Collings , Dominik Daisenberger , Christopher J. Ridley , Nicholas P. Funnell , Andrew Cairns Journal Of The American Chemical Society DOI: 10.1021/jacs.0c13181 Diamond Proposal Number(s): [19776] Open Access Show Abstract ▼ Abstract: The vast compositional space of Prussian blue analogues (PBAs), formula AxM[M′(CN)6]y·nH2O, allows for a diverse range of functionality. Yet, the interplay between composition and physical properties—e.g., flexibility and propensity for phase transitions—is still largely unknown, despite its fundamental and industrial relevance. Here we use variable-pressure X-ray and neutron diffraction to explore how key structural features, i.e., defects, hydration, and composition, influence the compressibility and phase behavior of PBAs. Defects enhance the flexibility, manifesting as a remarkably low bulk modulus (B0 ≈ 6 GPa) for defective PBAs. Interstitial water increases B0 and enables a pressure-induced phase transition in defective systems. Conversely, hydration does not alter the compressibility of stoichiometric MnPt(CN)6, but changes the high-pressure phase transitions, suggesting an interplay between low-energy distortions. AMnCo(CN)6 (AI = Rb, Cs) transition from F4̅3m to P4̅n2 upon compression due to octahedral tilting, and the critical pressure can be tuned by the A-site cation. At 1 GPa, the symmetry of Rb0.87Mn[Co(CN)6]0.91 is further lowered to the polar space group Pn by an improper ferroelectric mechanism. These fundamental insights aim to facilitate the rational design of PBAs for applications within a wide range of fields.	Feb 2021
I15-Extreme Conditions	Spin crossover in the Prussian blue analogue FePt(CN) 6 induced by pressure or X-ray irradiation Hanna L. B. Bostroem , Andrew B. Cairns , Lei Liu , Peter Lazor , Ines E. Collings Dalton Transactions 49, 12940 - 12944 DOI: 10.1039/D0DT02036B Diamond Proposal Number(s): [19776] Open Access Show Abstract ▼ Abstract: The spin state of the Prussian blue analogue FeIIPtIV(CN)6 is investigated in response to temperature, pressure, and X-ray irradiation. While cooling to 10 K maintains the high-spin state of FeII, compression at ambient temperature induces a first-order spin-crossover (SCO) transition with a small hysteresis loop (p↑ = 0.8 GPa, p↓ = 0.6 GPa). In addition, the high-spin to low-spin transition can be initiated at lower pressure through increased X-ray irradiation. Our study highlights a cooperative SCO with moderate pressure in a porous Prussian blue analogue.	Sep 2020
I15-Extreme Conditions	Encoding complexity within supramolecular analogues of frustrated magnets Andrew Cairns , Matthew Cliffe , Joseph Paddison , Dominik Daisenberger , Matthew G. Tucker , François-Xavier Coudert , Andrew L. Goodwin Nature Chemistry 8, 442 - 447 DOI: 10.1038/nchem.2462 Show Abstract ▼ Abstract: The solid phases of gold(I) and/or silver(I) cyanides are supramolecular assemblies of inorganic polymer chains in which the key structural degrees of freedom—namely, the relative vertical shifts of neighbouring chains—are mathematically equivalent to the phase angles of rotating planar (‘XY’) spins. Here, we show how the supramolecular interactions between chains can be tuned to mimic different magnetic interactions. In this way, the structures of gold(I) and/or silver(I) cyanides reflect the phase behaviour of triangular XY magnets. Complex magnetic states predicted for this family of magnets—including collective spin-vortices of relevance to data storage applications—are realized in the structural chemistry of these cyanide polymers. Our results demonstrate how chemically simple inorganic materials can behave as structural analogues of otherwise inaccessible ‘toy’ spin models and also how the theoretical understanding of those models allows control over collective (‘emergent’) phenomena in supramolecular systems.	May 2016
	Design of crystal-like aperiodic solids with selective disorder–phonon coupling Alistair R. Overy , Andrew B. Cairns , Matthew J. Cliffe , Arkadiy Simonov , Matthew G. Tucker , Andrew L. Goodwin Nature Communications 7 DOI: 10.1038/ncomms10445 PMID: 26842772 Open Access Show Abstract ▼ Abstract: Functional materials design normally focuses on structurally ordered systems because disorder is considered detrimental to many functional properties. Here we challenge this paradigm by showing that particular types of strongly correlated disorder can give rise to useful characteristics that are inaccessible to ordered states. A judicious combination of low-symmetry building unit and high-symmetry topological template leads to aperiodic ‘procrystalline’ solids that harbour this type of disorder. We identify key classes of procrystalline states together with their characteristic diffraction behaviour, and establish mappings onto known and target materials. The strongly correlated disorder found in these systems is associated with specific sets of modulation periodicities distributed throughout the Brillouin zone. Lattice dynamical calculations reveal selective disorder-driven phonon broadening that resembles the poorly understood ‘waterfall’ effect observed in relaxor ferroelectrics. This property of procrystalline solids suggests a mechanism by which strongly correlated topological disorder might allow independently optimized thermal and electronic transport behaviour, such as required for high-performance thermoelectrics.	Feb 2016
I15-Extreme Conditions	Competing hydrostatic compression mechanisms in nickel cyanide J. Adamson , T. C. Lucas , A. B. Cairns , N. P. Funnell , M. G. Tucker , A. K. Kleppe , J. A. Hriljac , A. L. Goodwin Physica B: Condensed Matter 479, 35 - 40 DOI: 10.1016/j.physb.2015.09.027 Show Abstract ▼ Abstract: We use variable-pressure neutron and X-ray diffraction measurements to determine the uniaxial and bulk compressibilities of nickel(II) cyanide, Ni(CN)2. Whereas other layered molecular framework materials are known to exhibit negative area compressibility, we find that Ni(CN)2 does not. We attribute this difference to the existence of low-energy in-plane tilt modes that provide a pressure-activated mechanism for layer contraction. The experimental bulk modulus we measure is about four times lower than that reported elsewhere on the basis of density functional theory methods.	Dec 2015
I15-Extreme Conditions	A comparison of the amorphization of zeolitic imidazolate frameworks (ZIFs) and aluminosilicate zeolites by ball-milling Emma F Baxter , Thomas D. Bennett , Andrew B. Cairns , Nick J. Brownbill , Andrew L. Goodwin , David A. Keen , Philip A Chater , Frédéric Blanc , Anthony K. Cheetham Dalton Transactions DOI: 10.1039/C5DT03477A PMID: 26575842 Diamond Proposal Number(s): [9691] Show Abstract ▼ Abstract: X-ray diffraction has been used to investigate the kinetics of amorphization through ball-milling at 20 Hz, for five zeolitic imidazolate frameworks (ZIFs) – ZIF-8, ZIF-4, ZIF-zni, BIF-1-Li and CdIF-1. We find that the rates of amorphization for the zinc-containing ZIFs increase with increasing solvent accessible volume (SAV) in the sequence ZIF-8 > ZIF-4 > ZIF-zni. The Li–B analogue of the dense ZIF-zni amorphizes more slowly than the corresponding zinc phase, with the behaviour showing a correlation with their relative bulk moduli and SAVs. The cadmium analogue of ZIF-8 (CdIF-1) amorphizes more rapidly than the zinc counterpart, which we ascribe primarily to its relatively weak M–N bonds as well as the higher SAV. The results for the ZIFs are compared to three classical zeolites – Na-X, Na-Y and ZSM-5 – with these taking up to four times longer to amorphize. The presence of adsorbed solvent in the pores is found to render both ZIF and zeolite frameworks more resistant to amorphization. X-ray total scattering measurements show that amorphous ZIF-zni is structurally indistinguishable from amorphous ZIF-4 with both structures retaining the same short-range order that is present in their crystalline precursors. By contrast, both X-ray total scattering measurements and 113Cd NMR measurements point to changes in the local environment of amorphous CdIF-1 compared with its crystalline CdIF-1 precursor	Nov 2015
I11-High Resolution Powder Diffraction	Compositional dependence of anomalous thermal expansion in perovskite-like ABX Ines E. Collings , Joshua A. Hill , Andrew B. Cairns , Richard I. Cooper , Amber L. Thompson , Julia E. Parker , Chiu C. Tang , Andrew L. Goodwin Dalton Transactions 45, 4169-4178 DOI: 10.1039/C5DT03263F PMID: 26477747 Diamond Proposal Number(s): [7907] Show Abstract ▼ Abstract: The compositional dependence of thermal expansion behaviour in 19 different perovskite-like metal–organic frameworks (MOFs) of composition [AI][MII(HCOO)3] (A = alkylammonium cation; M = octahedrally-coordinated divalent metal) is studied using variable-temperature X-ray powder diffraction measurements. While all systems show essentially the same type of thermomechanical response—irrespective of their particular structural details—the magnitude of this response is shown to be a function of AI and MII cation radii, as well as the molecular anisotropy of AI. Flexibility is maximised for large MII and small AI, while the shape of AI has implications for the direction of framework hingeing.	Oct 2015
I15-Extreme Conditions	Topochemical conversion of a dense metalorganic framework from a crystalline insulator to an amorphous semiconductor S. Tominaka , H. Hamoudi , T. Suga , T. D. Bennett , A. B. Cairns , A. K. Cheetham Chemical Science DOI: 10.1039/C4SC03295K Diamond Proposal Number(s): [9691] Show Abstract ▼ Abstract: The topochemical conversion of a dense, insulating metalorganic framework (MOF) into a semiconducting amorphous MOF is described. Treatment of single crystals of copper(I) chloride trithiocyanurate, CuI Cl(ttcH3) (ttcH3 ¼ trithiocyanuric acid), 1, in aqueous ammonia solution yields monoliths of amorphous CuI 1.8(ttc)0.6(ttcH3)0.4, 3. The treatment changes the transparent orange crystals of 1 into shiny black monoliths of 3 with retention of morphology, and moreover increases the electrical conductivity from insulating to semiconducting (conductivity of 3 ranges from 4.2 1011 S cm1 at 20 C to 7.6 109 S cm1 at 140 C; activation energy ¼ 0.59 eV; optical band gap ¼ 0.6 eV). The structure and properties of the amorphous conductor are fully characterized by AC impedance spectroscopy, X-ray photoelectron spectroscopy, X-ray pair distribution function analysis, infrared spectroscopy, diffuse reflectance spectroscopy, electron spin resonance spectroscopy, elemental analysis, thermogravimetric analysis, and theoretical calculations. Soli	Jan 2015
	Zero-strain reductive intercalation in a molecular framework Joshua Hill , Andrew B. Cairns , Jared J. K. Lim , Simon J. Cassidy , Simon J. Clarke , Andrew L. Goodwin Crystengcomm 17, 2925 - 2928 DOI: 10.1039/C4CE02364A Open Access Show Abstract ▼ Abstract: Reductive intercalation of potassium within the molecular framework Ag3[Fe(CN)6] gives rise to a volume strain that is an order of magnitude smaller than is typical for common ion-storage materials. We suggest that framework flexibility might be exploited as a general strategy for reducing cycling strain in battery and ion-storage materials.	Jan 2015

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