| 1. |
- Abbasi, Alireza, et al.
(författare)
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Highly hydrated cations : Deficiency, mobility and coordination of water in crystalline nonahydrated scandium(III), yttrium(III) and lanthanoid(III) trifluoromethanesulfonate
- 2005
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 11:14, s. 4065-4077
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Tidskriftsartikel (refereegranskat)abstract
- Trivalent lanthanide-like metal ions coordinate nine water oxygen atoms, which form a tricapped trigonal prism in a large number of crystalline hydrates. Water deficiency, randomly distributed over the capping positions, was found for the smallest metal ions in the isomorphous nonahydrated trifluoromethanesulfonates, [M(H2O)(n)]CF3SO3)(3), in which M=Sc-III, Lu-III, Yb-III, Tm-III or Er-III. The hydration number n increases (n=8.0(1), 8.4(1), 8.7(1), 8.8(1) and 8.96(5), respectively) with increasing ionic size. Deuterium (H-2) solid-state NMR spectroscopy revealed fast positional exchange between the coordinated capping and prism water molecules; this exchange started at temperatures higher than about 280 K for lutetium(m) and below 268 K for scandium(m). Similar positional exchange for the fully nonahydrated yttrium(m) and lanthanum(m) compounds started at higher temperatures, over about 330 and 360 K, respectively. An exchange mechanism is proposed that can exchange equatorial and capping water molecules within the restrictions of the crystal lattice, even for fully hydrated lanthanoid(III) ions. Phase transitions occurred for all the water-deficient compounds at; 185 K. The hydrated scandium(III) trifluoromethanesulfonate transforms reversibly (Delta H degrees= -0.80(1) kJ mol(-1) on cooling) to a trigonal unit cell that is almost nine times larger, with the scandium ion surrounded by seven fully occupied and two partly occupied oxygen atom positions in a distorted capped trigonal prism. The hydrogen bonding to the trifluoromethanesulfonate anions stabilises the trigonal prism of water ligands, even for the crowded hydration sphere of the smallest metal ions in the series. Implications for the Lewis acid catalytic activity of the hydrated scandium(III) and lanthanoid(III) trifluoromethanesulfonates for organic syntheses performed in aqueous media are discussed.
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| 2. |
- Christensen, Jeppe, 1975-
(författare)
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Non-Standard Crystallography : Examples in 3- and 3+1 Dimensional Space
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Crystallography today is by many seen as merely a tool for determining the structure of a material on the atomic level. It is expected that whatever comes out of the tool is the indisputable truth, a fact. This thesis is based on five publications illustrating that this is very far from the real world of materials research. The experiences drawn from the structural work in the papers are put together to illustrate when to be alert, and how to proceed with a structural investigation using non-standard crystallography. The focus is on interpreting the signs of additional order being present in a structure. The signs may be weak, such as extreme thermal vibration, or unit cell deformation. Or the signs can be strong, with superstructure reflections indicating the presence of either commensurate or incommensurate superstructures.
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| 3. |
- Christensen, Jeppe, et al.
(författare)
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Vacancy Ordering Effects in AlB2-type ErGe2-x(0.4 < x < or = 0.5)
- 2008
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Ingår i: Acta Crystallographica Section B. - 0108-7681 .- 1600-5740. ; 64:3, s. 272-280
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Tidskriftsartikel (refereegranskat)abstract
- In the Er-Ge system, the compostion range ErGe2 to Er2Ge3 has been investigated. Eight samples were produced by arc melting of the elements, and analyzed using X-ray powder diffraction. Nine crystal structures were found to be present in the samples. The structures are described as a homologous series and presented within the superspace formalism using the superspace group X2/m(0)0s, X representing the centring vector (½, ½, 0, ½). In this description the modulation vector q = (a* + c*) is shown to be a direct measure of the Ge content as ErGe2 - ( falls in the range to ½). The large composition range is achieved by extended vacancy ordering in the planar 63 net of Ge with subsequent relaxation.
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| 4. |
- Elenius, Måns, 1974-, et al.
(författare)
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Structural model for octagonal quasicrystals derived from octagonal symmetry elements arising in beta-Mn crystallization of a simple monatomic liquid
- 2009
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Ingår i: Physical Review B Condensed Matter. - Colllege Park, Maryland, USA : American Physical Society. - 0163-1829 .- 1095-3795. ; 79:14, s. 144201-
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Tidskriftsartikel (refereegranskat)abstract
- While performing molecular-dynamics simulations of a simple monatomic liquid, we observed the crystallization of a material displaying octagonal symmetry in its simulated diffraction pattern. Inspection of the atomic arrangements in the crystallization product reveals large grains of the beta-Mn structure aligned along a common fourfold axis, with 45° rotations between neighboring grains. These 45° rotations can be traced to the intercession of a second crystalline structure fused epitaxially to the beta-Mn domain surfaces, whose primitive cell has lattice parameters a=b=c=a_{beta-Mn}, alpha =beta =90°, and gamma =45°. This secondary phase adopts a structure which appears to have no known counterpart in the experimental literature, but can be simply derived from the Cr3Si and Al3Zr4 structure types. We used these observations as the basis for an atomistic structural model for octagonal quasicrystals, in which the beta-Mn and the secondary phase structure unit cells serve as square and rhombic tiles (in projection), respectively. Its diffraction pattern down the octagonal axis resembles those experimentally measured. The model is unique in being consistent with high-resolution electron microscopy images showing square and rhombic units with edge-lengths equal to that of the beta-Mn unit cell. Energy minimization of this configuration, using the same pair potential as above, results in an alternative octagonal quasiperiodic structure with the same tiling but a different atomic decoration and diffraction pattern.
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| 5. |
- Feuerbacher, Michael, et al.
(författare)
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The Samson phase, β-Mg2Al3, revisited
- 2007
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Ingår i: Zeitschrift fur Kristallographie. - : Walter de Gruyter GmbH. - 0044-2968. ; 222:6, s. 259-288
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Forskningsöversikt (refereegranskat)abstract
- The Al-Mg phase diagram has been reinvestigated in the vicinity of the stability range of the Samson phase, β-Mg2Al3 (cF1168). For the composition Mg38.5Al61.5, this cubic phase, space group Fd3̄m (no 227), a = 28.242(1) Å, V = 22526(2) Å3, undergoes at 214°C a first-order phase transition to rhombohedral β′-Mg2Al3, (hR293), a = 19.968(1) Å, c = 48.9114(8) Å, V = 16889(2) Å3, (i.e. 22519 Å3 for the equivalent cubic unit cell) space group R3m (no 160), a subgroup of index four of Fd3̄m. The structure of the β-phase has been redetermined at ambient temperature as well as in situ at 400°C. It essentially agrees with Samson's model, even in most of the many partially occupied and split positions. The structure of β′-Mg 2Al3 is closely related to that of the β-phase. Its atomic sites can be derived from those of the β-phase by group-theoretical considerations. The main difference between the two structures is that all atomic sites are fully occupied in case of the β′-phase. The reciprocal space, Bragg as well as diffuse scattering, has been explored as function of temperature and the β- to β′-phase transition was studied in detail. The microstructures of both phases have been analyzed by electron microscopy and X-ray topography showing them highly defective. Finally, the thermal expansion coefficients and elastic parameters have been determined. Their values are somewhere in between those of Al and Mg.
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| 6. |
- Flemström, Andreas, et al.
(författare)
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Inheritance of guanidinium chloride structure in two Molybdenum(II) chloride salts
- 2005
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Ingår i: Comptes rendus. Chimie. - : Elsevier SAS. - 1631-0748 .- 1878-1543. ; 8:11-12, s. 1750-1759
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Tidskriftsartikel (refereegranskat)abstract
- Depending on the proticity of the solvent, two different salts may be crystallized from the combination of solutions of guanidinium chloride, C(NH2)3Cl, and the acidic hydrate of molybdenum dichloride, [(Mo6Cl8)Cl6](H20O9). From aprotic solvents such as dimethyl sulfoxide (DMSO) or formamide (FA), compound I, [(Mo6Cl8)Cl6]Cl6(C(NH2)3)8, crystallizes, while from protic solvents such as ethanol or water, compound II, [(Mo6Cl8)Cl6]Cl3(C(NH2)3)5, crystallises. In both compounds, the basic motif of the two parent structures, the octahedral [(Mo6Cl8)Cl6]2– cluster and the planar, triangular, C(NH2)3Cl3 entity are fairly well preserved. The assembly of the blocks, however, differs distinctly, and while both compounds are rather porous, compound I (s.g. Fm m, No. 225) has a volume of 27 Å3/non-hydrogen atom, compound II (s.g. C2/c, No. 15) is somewhat denser, with a volume of 24 Å3/non-hydrogen atom.
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| 7. |
- Flemström, Andreas, 1968-
(författare)
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Solide Molydbenum(II) Chloride Cluster compounds From a Hudrogen Bonding Poin of View
- 2005
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis is based on a study of solid Molybdenum(II) chloride cluster compounds. The emphasis of the text is on the hydrogen network in the different compounds. The main analysis tool has been single crystal x-ray diffraction, and in some cases theoretical calculations have been performed to confirm the hydrogen positions.It has been shown that the Mo(II) cluster is a very good promoter for hydrogen bonds. The hydrogen bond networks studied here are fairly rigid and strong, except for one compound where the easy loss of a water molecule changes the water structure dramatically.There are several ways to alter the crystal structure and of course alter the hydrogen bond network.Ø Change the syntheses with respect to pHØ Change the apical halogenidesØ Introducing cations instead of H3O+Ø Using protonated organic amino bases as cations and different organic solventsAll of these methods have been tested and evaluated. The general conclusion is that the cluster units are nicely ordered in the hydrogen bond network.
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| 8. |
- Fredrickson, Daniel C., et al.
(författare)
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The Origins of Superstructure Ordering and Incommensurability in Stuffed CoSn-type Phases
- 2008
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society. - 0002-7863 .- 1520-5126. ; 130:26, s. 8195-8214
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Tidskriftsartikel (refereegranskat)abstract
- The CoSn structure type contains large interstitial void spaces that frequently host electropositive guest atoms, such as rare earth elements. In this stuffing process, an intriguing ordering occurs between the neighboring void spaces leading to a family of long-period superstructures comprising intergrowths of the ScFe6Ge6 and ScFe6Ga6 structure types. This superstucture ordering culminates in incommensurability in the REFe6Ge6–δGaδ systems with RE = Sc, Tb, and Lu. In this work, we derive a 3 + 1D superspace model encompassing this series of structures and investigate the origins of the structural trends in this family with electronic structure calculations, at both the LDA-DFT and extended Hckel levels. Using our 3 + 1D model, we refine the structures of four new ErFe6Ge6−δGaδ (0 ≤ δ ≤ 6) phases, two commensurate and two incommensurate, from powder X-ray diffraction data. The refinement results confirm trends observed in the Sc-, Tb-, and Lu-based series: a gradual lengthening and, eventually, turning of the q-vector as Ge is progressively exchanged for Ga. These trends, and the incommensurate ordering as a whole, are traced to a tension between two modes by which the host lattice responds to stuffing atom insertion: (1) an atomic charge modulation enhancing the anionic character of the cavity walls around the guest atoms, and (2) a positional modulation expanding the cavities occupied by guest atoms. These two modes direct the stuffing atom ordering pattern toward opposite ends of the ScFe6Ge6−ScFe6Ga6 intergrowth series. The full series of structures, complex and incommensurate, reflects various degrees of balance between these two factors.
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| 9. |
- Fredrickson, Daniel, et al.
(författare)
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Re4Si7, First in a New MoSi2-Based Family of 14-Electron Phases
- 2009
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 15:33, s. 8108-8112
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Tidskriftsartikel (refereegranskat)abstract
- The compound Re4Si7 poses a long-standing structural mystery at the intersection of the quantum chemical and material properties areas of interest. Its atomic structure has gradually emerged over X-ray and electron diffraction studies since 1941 to be a complex ordering of Si vacancies on a MoSi2-type lattice, the details of which remain unresolved. In 1941, it was originally identified as ReSi2, adopting the MoSi2-type crystal structure (Figure 1).1a In this structure, Re atoms form a body-centered tetragonal lattice, while the Si atoms lie in the square-pyramidal interstitial spaces of this Re lattice. This was followed by two structure reports in progressively lower symmetry: an orthorhombic Immm solution (1983),1b and a triclinic P1 solution (1995),1c in which fractional occupancies on the Si sites adjust the composition to the Re4Si7 stoichiometry reported in a redetermination of the Re–Si phase diagram.1d Electron microscopy investigations then revealed complex superstructures and incommensurability in Re4Si7 samples.2 This work culminated in an attempt to solve its structure as an eight-fold supercell in the space group Cm from single-crystal synchrotron X-ray diffraction data (2004).1e Severe refinement instabilities were encountered, and the published structure shows chemically implausible Re–Si and Si–Si distances
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| 10. |
- Fredrickson, Rie Takagi, 1981-
(författare)
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A new synthetic strategy for low-dimensional compounds : Lone pair cations and alkaline earth spacers
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Complex transition metals oxyhalides containing a lone pair element, such as tellurium (IV), form an attractive research field because there is a high probability of finding new low-dimensionally arranged compounds and, particularly, a low-dimensionally arranged transition metals substructures, leading to interesting physical properties. Tellurium (IV) can drive the formation of many unusual structures because of its stereochemically active lone pair electrons, E. It commonly takes a coordination of three or four oxygen atoms to form either a TeO3E square pyramid or a TeO3+1E trigonal bipyramid. These lone pairs are very important players involved in lowering the dimensionality of crystal structures. Previous studies in transition metal tellurium (IV) oxohalide quarternary systems revealed a family of compounds, many of which exhibit interesting properties e.g. magnetic frustration. The unique point of this thesis is to employ alkaline earth elements (AE) to augment this ability of lone pair elements to lower the dimensionality of the transition metal arrangements. By this double usage of “chemical scissors” (a lone pair element used in conjunction with alkaline earth elements) we obtained new types of low-dimensionally arranged compounds.This thesis is focused on the syntheses and characterization of a series of compounds in the pentanary (five components) system AE-TeIV-TM-O-X (AE=alkaline earth metal, TM=transition metal and X=halogen), in which nine new compounds were found. The crystal structures of each of these compounds were determined by the single crystal X-ray diffraction data.
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