12,575 research outputs found
Synthesis and coordination chemistry of hybrid polydentate and halide-substituted stibines and bismuthines
No full textHalostibines and halobismuthines EMenX3-n (E = Sb, Bi; X = Cl, Br; n = 1, 2) display both Lewis acidic and Lewis basic characteristics. A series of adducts with neutral N- and O-donor ligands, [EMeX2(L)] (L = 2,2’-bipyridine, 1,10-phenanthroline, tetramethylethylenediamine) and [SbMeX2(L)2] (L = Ph3PO, Me3PO) were isolated and characterised by X-ray crystallography, 1H (and where appropriate 31P{1H}) NMR spectroscopy and microanalysis. Each complex is monomeric, displaying a distorted square pyramidal geometry around E, with two basal cis halides and the Me group apical. Combination of EMe2X with neutral ligands results in rearrangement at E to yield [EMeX2(L)] or [SbMeX2(L)2] once again as the isolable products. Reaction of SbMenBr3-n (n = 1, 2) with transition metal acceptors gives complexes in which the halostibines behave as Lewis bases. Examination of trends in the crystallographic and spectroscopic data of [M(CO)5(SbMenBr3-n)] (M = Cr, W; n = 1-3) from this work and the literature concluded that the halostibines have a significant ?-acceptor ability, which increases with increased halide substitution. Other transition metal complexes with L = SbMe2Br, [CpFe(CO)2(L)][BF4], [CpFe(CO)(L)2]Br (Cp = cyclopentadienyl) and [Mn(CO)6-n(L)n][CF3SO3] (n = 1, 3) were isolated and contain hypervalent, Sb···O, Sb···F or Sb···Br contacts between ions. Reaction of BiMe2Br with transition metal acceptors results in rearrangement at Bi; the only bismuthine complexes isolated contained the BiMe3 ligand.The hybrid distibine S(CH2-2-C6H4SbMe2)2 and its methiodide [S(CH2-2-C6H4SbMe3)2][I]2 were synthesised and the X-ray structure of the latter determined. Systematic investigations into transition metal complexes of this and other hybrid distibine ligands were undertaken. These ligands coordinate in a bidentate bridging mode in the 1:2 complexes [{CpFe(CO)2}2(L)][BF4] (L = O{(CH2)2SbR2}2 (R = Me, Ph), MeN(CH2-2-C6H4SbMe2)2, S(CH2-2-C6H4SbMe2)2) and [{M(CO)5}2(L)] (M = Cr, W; L = O{(CH2)2SbR2}2 (R = Me, Ph)), a bidentate chelating mode in [M(CO)4(L)] (M = Cr, W; L = O{(CH2)2SbMe2}2, MeN(CH2-2-C6H4SbMe2)2) or a tridentate mode in [M(CO)3(S(CH2-2-C6H4SbMe2)2)] (M = Cr, Mo) and [Mn(CO)3(L)] [CF3SO3] (L = MeN(CH2-2-C6H4SbMe2)2, S(CH2-2-C6H4SbMe2)2). In the latter examples the central hetero-atom of the ligand is coordinated to the transition metal centre. In those cases where it is not, hypervalent interactions between this hetero-atom and one or both coordinated Sb atoms are sometimes, but not always, observed. Comparisons have been drawn with the chemistry of the corresponding hybrid dibismuthine ligands. The hybrid tristibine ligand N(CH2-2-C6H4SbMe2)3 was synthesised and preliminary investigations of its coordination chemistry carried out. It acts as a tridentate ligand via the three Sb donors in [Mn(CO)3(L)][CF3SO3] and [Cu4Br4(L)2], with the ligand fixed in a propeller-like conformation. In the latter, a Cu2Br4 core with a short Cu···Cu distance is observed. [Cu(L)] [BF4] was isolated, in which tetradentate coordination of the ligand has been proposed.Transition metal complexes were characterised by 1H and 13C{1H} NMR spectroscopy and microanalysis, and where appropriate infrared and 55Mn or 63Cu NMR spectroscopies and mass spectrometry. The majority of these complexes have also been structurally characterised by single crystal X-ray diffraction
Disorder in Extra-Large Pore Zeolite ITQ-33 Revealed by Single Crystal XRD
No full textThe single crystal of the extra-large pore zeolite, ITQ-33, was obtained and used to explore its crystal structure details. The ITQ-33 structure was found to be disordered with the columnar periodic building unit, explaining the morphology changes upon the different Si/Ge ratio, and the formation of the hierarchical structure from assembling of ITQ-33 nanofibers.Chemistry, MultidisciplinaryCrystallographyMaterials Science, MultidisciplinarySCI(E)EI0ARTICLE104168-41711
crystal-torture: A crystal tortuosity module
No full text<p>crystal_torture: A crystal structure analysis code, allowing site tortuosity to be calculated.</p>This work was funded by EPSRC Grant No. EP/N004302/1, and was supported with fund-
ing from the Faraday Institution (faraday.ac.uk; EP/S003053/1), grant number FIRG003.
B.J.M. acknowledges support from the Royal Society (UF130329)
Liquid crystal adaptive planar optical devices
No full textThis thesis presents a series of experimental studies based on using liquid crystals (LC) with planar optical lightwave components. Adaptive optical devices have been fabricated by combining LCs with direct UV written buried channel waveguide and Bragg grating structures. It has been discovered that the hysteresis seen in previous LC tunable Bragg grating devices is due to a process known as the pincement transition. Pincement involves the transition from a splay-bend wall in the nematic LC to a pair of oppositely charged half-integer disclination lines. The voltage-based transient behaviour of the pincement transition correlated with the tuning curve response seen in voltage controlled LC tunable gratings. In order to reduce the hysteresis effect a new grooved substrate geometry was introduced. Rather than accessing the Bragg grating vertically via a wet etch process, the substrates are precision machined using a dicing saw to allow side access. The result is significantly reduced hysteresis, with a maximum tuning range of over 1nm with the application of under 30V(pp). Tunable chirped Bragg gratings based on standard PCB technology using arrays of resistors as heating elements were designed and tested. The group delay slope of the chirped gratings was tuned by 4ps/nm using a combination of heating elements and thermoelectric cooling. Finally, LC compounds were then tested for suitability as waveguiding media. It was found that both hollow fiber and planar substrate systems using an LC as the core guiding medium successfully guided both visible and IR light at telecomms wavelength
An essay on the nature and wonderful properties of Island Crystal : respecting its manifold and unusual refraction of light
No full text[Benjamin Martin]Urheber und Erscheinungsvermerk nach EST
Hanging the harp on the willow tree: music and national identity in postcolonial Ireland
No full textAn inquiry into how music served as a nation building tool in the early decades of the Irish Free State.M.A.Includes bibliographical referencesby Crystal N. Galyea
Investigation of nucleation and crystal growth kinetics of nickel manganese oxalates
No full textThe nucleation and the crystal growth rates of mixed nickel manganese oxalates have been determined from the changes of the ionic concentration of the solution and the crystal size distribution during the precipitation process within a supersaturation range 0–0.1 M. Thermodynamic solubility calculations have been used to identify the different species contributing the precipitation reaction and for estimation of the thermodynamic constant. Experimental data show that the nucleation rate of mixed nickel manganese oxalate in this supersaturation range is consistent with a primary heterogeneous mechanism and was found to obey to an exponential law. The crystal growth rates indicate a surface-integration-controlled mechanism with a first-order law with respect to the supersaturation
Thin aligned organic polymer films for liquid crystal devices
No full textThis project was designed to investigate the possibility of producing alignment layers for liquid crystal devices by cross-linking thin films containing anisotropic polymer bound chromophores via irradiation with polarised ultra violet light. Photocross-linkable polymers find use in microelectronics, liquid crystal displays, printing and UV curable lacquers and inks; so there is an increasing incentive for the development of new varieties of photopolymers in general. The synthesis and characterisation of two new photopolymers that are suitable as potential alignment layers for liquid crystal devices are reported in this thesis. The first polymer contains the anthracene chromophore attached via a spacer unit to a methacrylate backbone and the second used a similarly attached aryl azide group. Copolymers of the new monomers with methyl methacrylate were investigated to establish reactivity ratios in order to understand composition drift during polymerisation
Finite element method for 3D optical modeling of liquid crystal on silicon spatial light modulator
No full textAccurate optical modeling for design and optimization of liquid crystal on silicon spatial light modulators (LCoS SLMs) is important for phase-related applications. Traditional matrix method cannot accurately predict the optical performance when the LC distribution is complex, therefore the rigorous finite element method (FEM) is preferred. However, the optical modeling of LCoS is a multidimensional problem, which is difficult to simulate with FEM. Here, we present the development of an improved FEM by combining the scattering matrix method with the domain decomposition method to reduce the computational burden for optical simulation of LCoS. Furthermore, a 2D simulation example with phase grating displayed on LCoS is presented and compared with experiment.Grant ID: ColoOpt- EU H2020 ITN 721465ImPhys/Optic
Gel-mediated chemo-mechanical control of calcium carbonate crystal formation
No full textThe production of synthetic crystals with controlled shapes and properties is an enticing prospect, yet, the production of such materials is an ongoing challenge. Here, we present a strategy for chemo-mechanically directing the growth of crystals with non-equilibrium structures using a custom-designed double-diffusion cell. We combine chemical additives (e.g., Mg2+ ions) and mechanical confinement (e.g., hydrogel networks) to modulate the growth of calcium carbonate crystals. Specifically, the combination of Mg2+ ions with a strong agarose gel results in calcitic structures, at the gel-glass slide interface, with distinct fried egg-like morphologies and radial or Maltese-cross extinction patterns. In contrast, precipitation with only Mg2+ or agarose results in aragonite spherulites or squished calcite rhombohedra, respectively. Raman spectroscopy and energy dispersive spectroscopy of the “fried eggs” reveals that they are composed of Mg-calcite, which becomes less disordered over time, and the “egg whites” make this transition before the “yolks”. We propose that the “fried eggs” form due to a spherulitic growth process molded by the crystallization-induced delamination of the gel away from the glass slide at the gel-glass interface. In support of the importance of the gel-glass interface, the “fried eggs” do not form when the glass slide is treated with a hydrophobic silane, suppressing heterogeneous nucleation and weakening the interfacial adhesion between the gel and glass, making it easier for the gel to delaminate, thus reducing the confinement effect. As such, this work highlights the important chemo-mechanical role that gel environments can play in crystal formation.Green Open Access added to TU Delft Institutional Repository 'You share, we take care!' - Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.Materials and Environmen
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