Browsing by Subject "Clathrate compounds"

Now showing 1 - 6 of 6
  • Thumbnail Image
    Item
    Open Access
    DNA-mediated biomineralization of a new planar Pt-complex
    (2006) Klump, H H; Koch, K; Lin, C T
    The crystal growth morphology of a coordination complex of Pt(II) that crystallizes from solution can be controlled by using a second molecular species such as peptides or other organic compounds. Examples of crystal growth controlled by nucleic acids are few. In this article we describe the use of branched three-way junction (3WJ) DNA to influence the crystal growth of a planar platinum compound, cis-[(2, 2′-bipyridyl)N,N-di(2-hydroxyethyl)-N′-benzoylthioureatoplatinum(II)]chloride. Platinum complexes with extended planar aromatic residues are capable of stacking in the absence as well as in the presence of linear DNA double helices. This feature is based on the interaction of the compound with DNA through intercalation, resulting in the prevention of binding of DNA polymerase. Microscopic one-dimensional crystals were observed under these conditions. In the presence of the branched 3WJ DNA, however, additional nucleation sites are present, resulting in extended crystal growth of unique Pt compounds. At least two different crystal modifications were observed using transmission electron microscopy.
  • Thumbnail Image
    Item
    Open Access
    Selective criteria in Werner clathrates
    (1988) Lavelle, Laurence
    We have elucidated the structures of a series of Werner Clathrates with systematically changing guest molecules. The host is the inorganic coordination compound bis(isothiocyanato)tetra(4-vinylpyridine)nickel(II), [Ni(NCS)2(4-ViPy)4]. The guests are mixtures of tetrahydrofuran and the cyclic hydrocarbons: cyclohexane, cyclohexene, 1,3-cYclohexadiene, 1,4-cyclohexadiene and benzene. Host to guest ratios were elucidated by density and proton nuclear magnetic resonance spectroscopy. The thermal characteristics of the compounds were analysed by thermogravimetric analysis and differen.tial thermal analysis. The structures of two related compounds [Ni(NCS)2(Py)4] and [Ni(NCS)2(Py)4].nbenzene were also studied.
  • Thumbnail Image
    Item
    Open Access
    Structure-activity relationships in Werner clathrates
    (1987) Moore, Madeleine Henrietta; Nassimbeni, Luigi R
    The synthesis and characterization of a series of inorganic coordination compounds which, upon crystallization, have the ability to include solvent or guest molecules spatially within the lattice are reported. The compounds have the following general formula: [NiX2B4] - where X is isothiocyanate or bromine and B is 4-ethylpyridine, 4-vinylpiridine or 3,5-dimethylpyridine; [NiX2B2]n - where X is isothiocyanate, B is 2-aminopyridine and n indicates it is a polymer; [NiX2AB2]2 - where X is isothiocyanate, B is 3-aminopyridine (two of these four ligands in the dimer are bridging) and A is water. The various guest molecules have been carefully chosen, according to their point symmetry, which is a key factor in yielding structures of a particular type. The structures of seventeen compounds have been elucidated by single crystal x-ray analysis. The difficulty has been found to lie in refining disordered guest molecules. Other techniques employed in the initial characterization of these compounds are Microanalysis, Mass Spectrometry and UV/Visible Spectrophotometry. An intramolecular potential energy study on the [Ni(NCS)2(3,5-diMepy)4] complex reveals that the orthohydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. Packing densities and volume comparisons of the [Ni(NCS)2(4-Etpy)4] and [Ni(NCS)2(4-Vipy)4] complexes and their clathrates have been carried out. The exact sizes and shapes of the cavities in which the guest molecules are located in the x-ray crystal structures have been evaluated by both intermolecular potential energy and molecular volume calculations. Thermodynamic and spectroscopic properties of the [Ni(NCS)2(4-Etpy)4] and [Ni(NCS)2(4-Vipy)4] clathrates have been studied in both solution and the solid state. The techniques used are x-ray powder diffractometry, IR spectroscopy and Thermogravimetry (including Differential Thermal Analysis).
  • Thumbnail Image
    Item
    Open Access
    Structures of Werner clathrates
    (1983) Papanicolaou, Sevasti; Nassimbeni, Luigi R
    X-ray crystallographic studies have been used to elucidate the structures of two new Werner clathrates. ... The chloroform molecule is disordered, lying on a two-fold axis. Stoicheiometric characterization of the clathrates was determined using various chemical techniques, including mass spectroscopy, proton nuclear magnetic resonance and complex iometric titration. The clathrating phase of the second clathrate was investigated by guest-loss studies on a McBain balance followed by X-ray powder photography. Host-quest non-bonded interactions of both clathrate compounds were studied using atom-pair potentials.
  • Thumbnail Image
    Item
    Open Access
    Structures of Werner clathrates
    (1989) Taylor, Michael William; Nassimbeni, Luigi R
    This work is predominantly devoted to the 4-phenylpyridine ligand and the role that it plays in the formation of a series of inorganic coordination complexes termed Werner Clathrates. The synthesis and characterization by single crystal X-ray diffraction techniques are reported for 18 structures, the majority of which, upon crystallization, have the ability to include solvent or guest molecules within the host framework. The compounds are divided into four broad classes with the host complex of each as follows: Class A [Ni(NCS)₂(4-PhPy)₄]; Class B [NiCl₂(4-PhPy)₄]; Class c [Ni(NCS)₂(4-MePy)₂(4-PhPy)₂]; Class D [NiX₂(dmso)₂(4-PhPy)₂] where X= Ncs- or Cland [Ni(NCS)₂(4-RPy)₄] where R = 4-t-Bu or 4-Bz. The guest molecules, anionic ligand and substituent on the pyridine ligand have all been varied to try to establish the role that they each play in the formation of a structure. Much effort has been spent on the location and refinement of disordered guest molecules. Use has been made of statistical disorder and molecular scattering factors to try and successfully model these guests. The shapes of the cavities containing the guest molecules have been mapped by volume calculations and comparisons made between the packing of the compounds. Several of the complexes pack in space groups which are subsets of others and attempts have been made to determine the cause of the reduction in symmetry. A new technique to analyze competition experiments, with two guest solvents competing for occupation of the voids within the host lattice, has been established. Preliminary results for competition between p-xylene/benzene, p-xylene/toluene and p-xylene/ethylbenzene with the host complex [Ni(NCS)₂(4-ViPy)₄] are reported. The ability of the host complex [Ni(NCS)₂(4-MePy)₂(4-PhPy)₂] to separate a series of straight chain alcohols is demonstrated. The preference, by this host complex, for guest molecules containing a linear skeleton of 5 non-hydrogen atoms, is explained in terms of potential energy and residual volume calculations. Thermal analysis, consisting of thermogravimetry and differential thermal analysis, has been performed on several of the compounds. Temperatures of guest release, host decomposition and the enthalpies involved at each of these steps are reported.
  • Thumbnail Image
    Item
    Open Access
    A study of secondary bonding effects in Werner clathrates
    (1988) Suckling, Adrian Philip; Nassimbeni, Luigi R; Niven, Margaret Lilian
    The crystal structures of Ni(NCS)₂(4-ViPy)₂.nG where nG = 2CH₂Cl₂ (I), 2CCl₄ (II), 1.8CH₂I₂ (III) and CHI₃ (IV), as well as the crystal structure of [Ni(NCS)₂(4-ViPy)₄]. [Ni(NCS)₂(4-ViPy)₃(thf)].2CHI₃ (V) have been elucidated. The diiodomethane guest molecules in STRUCTURE III were severely disordered at room temperature and so this structure was solved at -40°C. The dichloromethane clathrate is isomorphous with the chloroform clathrate of the same host, and both these clathrates have a similar packing to the carbon tetrachloride clathrate. There is significant secondary bonding between the sulphur (donor) of the isothiocyanate ligand of the host and the iodines (acceptor) of the halogenated guest molecules in compounds III, IV and V. The iodoform clathrates, compounds IV and V, also show strong similarities in their packings. Particular attention has been paid to the shape and size of the cavities in which the guest molecules find themselves, in order to gain a better understanding of the nature of these clathrates. This has also shed some light on the probable cause of the disordered diiodomethane molecules in STRUCTURE III. Packing densities and volume comparisons of the [Ni(NCS)₂(4-ViPy)₂] clathrates have been carried out. Solid - state U.V/visible spectroscopy was used to obtain information on the host conformation, and thermal analysis (thermogravimatry and differential thermal analysis) was used to obtain insight into the host - guest interactions of these clathrates.