Search results for "Halogens"
showing 10 items of 24 documents
Bamboo-like Chained Cavities and Other Halogen-Bonded Complexes from Tetrahaloethynyl Cavitands with Simple Ditopic Halogen Bond Acceptors
2018
Halogen bonding provides a useful complement to hydrogen bonding and metal-coordination as a tool for organizing supramolecular systems. Resorcinarenes, tetrameric bowl-shaped cavitands, have been previously shown to function as efficient scaffolds for generating dimeric capsules in both solution and solid-phase, and complicated one-, two-, and three-dimensional frameworks in the solid phase. Tetrahaloethynyl resorcinarenes (bromide and iodide) position the halogen atoms in a very promising “crown-like” orientation for acting as organizing halogen-bond donors to help build capsules and higher-order networks. Symmetric divalent halogen bond acceptors including bipyridines, 1,4-dioxane, and 1…
Factors Governing the Chemical Stability and NMR Parameters of Uracil Tautomers and Its 5-Halogen Derivatives
2020
We report on the density functional theory (DFT) modelling of structural, energetic and NMR parameters of uracil and its derivatives (5-halogenouracil (5XU), X = F, Cl, Br and I) in vacuum and in water using the polarizable continuum model (PCM) and the solvent model density (SMD) approach. On the basis of the obtained results, we conclude that the intramolecular electrostatic interactions are the main factors governing the stability of the six tautomeric forms of uracil and 5XU. Two indices of aromaticity, the harmonic oscillator model of aromaticity (HOMA), satisfying the geometric criterion, and the nuclear independent chemical shift (NICS), were applied to evaluate the aromaticity of ur…
New insight into halogen release from experimental studies on BrO/Br ratios in volcanic plumes
2014
Surface-relief gratings in halogen-bonded polymer-azobenzene complexes A concentration-dependence study
2017
In recent years, supramolecular complexes comprising a poly(4-vinylpyridine) backbone and azobenzene-based halogen bond donors have emerged as a promising class of materials for the inscription of light-induced surface-relief gratings (SRGs). The studies up to date have focused on building supramolecular hierarchies, i.e., optimizing the polymer–azobenzene noncovalent interaction for efficient surface patterning. They have been conducted using systems with relatively low azobenzene content, and little is known about the concentration dependence of SRG formation in halogen-bonded polymer–azobenzene complexes. Herein, we bridge this gap, and study the concentration dependence of SRG formation…
Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin-Crossover Coordination Polymer
2009
Capillary electrophoretic and nuclear magnetic resonance studies of interactions between halophenols and ionic liquid or tetraalkylammonium cations.
2003
Aqueous capillary electrophoretic studies were performed to investigate interactions between halophenols and 1-ethyl-3-methylimidazolium tetrafluoroborate or tetraethylammonium tetrafluoroborate electrolytes. In both cases, increased halogen size correlated with increased affinity for the electrolyte cation. For isomers, the ortho substituted isomer exhibited higher affinity than the para isomer. Irreproducible CE results for analyte pairs in the presence of the ionic liquid stimulated investigations of the interactions between halophenols as well as with the cations of the electrolyte. These interactions were explored by proton and fluorine one-dimensional NMR. The NMR results indicated di…
Synthesis and Characterisation of Chiral Triazole-Based Halogen-Bond Donors: Halogen Bonds in the Solid State and in Solution
2017
A general platform for the synthesis of various chiral halogen-bond (XB) donors based on the triazole core and the characterisation of factors that influence the strength of the halogen bond in the solid state and in solution are reported. The characterisation of XB donors in the solid state by X-ray crystallography and in solution by 1H NMR titration can be used to aid the design of new XB donors. We describe the first example of a XB between iodotriazoles and thioureas in solution. In addition, the enantiodiscrimination of acceptors in solution through halogen-bond participation is described.
Halogen bond preferences of thiocyanate ligand coordinated to Ru(II) via sulphur atom
2017
Halogen bonding between [Ru(bpy)(CO)2(S-SCN)2] (bpy = 2,2’-bipyridine), I2 was studied by co-crystallising the metal compound and diiodine from dichloromethane. The only observed crystalline product was found to be [Ru(bpy)(CO)2(S-SCN)2]⋅I2 with only one NCS⋅⋅⋅I2 halogen bond between I2 and the metal coordinated S atom of one of the thiocyanate ligand. The dangling nitrogen atoms were not involved in halogen bonding. However, computational analysis suggests that there are no major energetic differences between the NCS⋅⋅⋅I2 and SCN⋅⋅⋅I2 bonding modes. The reason for the observed NCS⋅⋅⋅I2 mode lies most probably in the more favourable packing effects rather than energetic preferences between …
Halogens in volcanic systems
2009
The transport, degassing and atmospheric release of halogens from active volcanism on Earth have been the 12 focus of increasing interest over the last few decades, and have recently been the subject of the 1st workshop 13 on “Halogens in volcanic systems and their environmental impacts” that was held in December of 2007 at 14 Yosemite Lodge in Yosemite National Park, California. As an introduction to this Chemical Geology special 15 issue, collecting contributions from many of the participants at the workshop, we review here recent 16 advances in this field, including experimental and theoretical investigations of halogen behaviour in volcanic 17 and related magmatic systems. We discuss pr…