Search results for "Halogen"
showing 10 items of 434 documents
Solid‐state NMR Spectroscopy of Iodine(I) Complexes
2023
Solid-state NMR has been applied to a series of Barluenga-type iodine(I) [L-I-L]PF6 (L=pyridine, 4-ethylpyridine, 4-dimethylaminopyridine, isoquinoline) complexes as their hexafluorophosphate salts, as well as their respective non-liquid ligands (L), their precursor silver(I) complexes, and the respective N-methylated pyridinium and quinolinium hexafluorophoshate salts. These results are compared and contrasted to the corresponding solution studies and single-crystal X-ray structures. As the first study of its kind on the solid-state NMR behavior of halogen(I) complexes, practical considerations are also discussed to encourage wider utilization of this technique in the future. peerReviewed
Iodine Clathrated : A Solid-State Analog of the Iodine-Starch Complex
2019
Co-crystallizing iodine with a simple dicationic salt (1,8- diammoniumoctane chloride) results in the clathration of the iodine (I2) molecules inside trigonal and hexagonal helical channels of the crystal lattice with 72 wt% overall I2 loading. The I2 inside the bigger trigonal channel forms a I-I•••I-I•••I-I halogen-bonded infinite helical chain, while the I2 in the smaller hexagonal channel is disordered. In both channels the I2 interaction with the channel wall happens through I-I•••Cl- halogen bonds. The helical channels in the crystal lattice are constructed via the strong charge-assisted H2N+ -H•••Cl- hydrogen bonds between the dications and the chloride anions. The structure shows a …
Charge-Assisted Halogen Bonding in an Ionic Cavity of a Coordination Cage Based on a Copper(I) Iodide Cluster.
2023
The design of molecular containers capable of selective binding of specific guest molecules presents an interesting synthetic challenge in supramolecular chemistry. Here, we report the synthesis and structure of a coordination cage assembled from Cu3I4– clusters and tripodal cationic N-donor ligands. Owing to the localized permanent charges in the ligand core the cage binds iodide anions in specific regions within the cage by ionic interactions. This allows the selective binding of bromomethanes as secondary guest species within cage promoted by halogen bonding, which was confirmed by single crystal X-ray diffraction. peerReviewed
Do 2-coordinate iodine(I) and silver(I) complexes form Nucleophilic Iodonium Interactions (NIIs) in solution?
2022
The interaction of a [bis(pyridine)iodine(I)]+ cation with a [bis(pyridine)silver(I)]+ cation, in which an iodonium ion acts as nucleophile by transferring electron density to the silver(I) cation, is reinvestigated herein. No measurable interaction is observed between the cationic species in solution by NMR; DFT reveals that if there is an attractive interaction between this complexes in solution, it is dominantly the π-π interaction of pyridines peerReviewed
The S … Hal and Se … Hal chalcogen bonding in a series of thiourea, selenourea and their derivatives
2021
The chalcogen bonding (ChB) in a series of thiourea, selenourea and their derivatives has been investigated in the present paper. Thus, selenourea and dimethylselenourea undergo dimerization and trimerization processes in the presence of various halogen species (1–5). Selenourea and dimethylselenourea form trimers 3–4 in the presence of lighter halogens (chlorine and bromine) through Se⋯Se chalcogen bonding. When moving to heavier halogen (iodine), the dimers 1–2 are formed. Thiourea and its derivatives also tend to make very strong S⋯S bonds and form dimers in the case of lighter halogens chlorine and bromine (compounds 6–7). However, the monomers separated by the iodine species are formed…
Halogen Bonding between Thiocarbonyl Compounds and 1,2- and 1,4-Diiodotetrafluorobenzenes
2021
The halogen bonding (XB) between 1,2-diiodotetrafluorobenzene (1,2-DITFB) or 1,4-diiodotetrafluorobenzene (1,4-DITFB) and the selection of different thiocarbonyl acceptors was studied by the single-crystal X-ray diffraction method. Diiodotetrafluorobenzenes (DITFBs) were found to form C-I···S halogen-bonded 1:1, 2:1, and 1:2 (donor/acceptor ratio) complexes with thiocarbonyls. Lengths of contacts were found to be clearly shorter than the sum of van der Waals radii of iodine and sulfur as well as the contact angles showed values close to linear, so the XB interactions could be verified. One sulfur atom showed the ability to accept one, two, or four XB interactions, and the acceptor angle can…
Extended Assemblies of Ru(bpy)(CO)2X2 (X = Cl, Br, I) Molecules Linked by 1,4-Diiodotetrafluoro-Benzene (DITFB) Halogen Bond Donors
2019
The ruthenium carbonyl compounds, Ru(bpy)(CO)2X2 (X = Cl, Br or I) act as neutral halogen bond (XB) acceptors when co-crystallized with 1,4-diiodotetrafluoro-benzene (DITFB). The halogen bonding strength of the Ru-X&sdot
Tridentate C–I⋯O−–N+ halogen bonds
2017
The X-ray structures of the first co-crystals where the three oxygen lone pairs in N-oxides are fully utilized for tridentate C–I⋯O−–N+ halogen bonding with 1,ω-diiodoperfluoroalkanes are reported, studied computationally, and compared with the corresponding silver(I) N-oxide complexes. peerReviewed
A Novel Halogen Bond Acceptor : 1-(4-Pyridyl)-4-Thiopyridine (PTP) Zwitterion
2020
Sulfur is a widely used halogen bond (XB) acceptor, but only a limited number of neutral XB acceptors with bifurcated sp3-S sites have been reported. In this work a new bidentate XB acceptor, 1-(4-pyridyl)-4-thiopyridine (PTP), which combines sp3-S and sp2-N acceptor sites, is introduced. Three halogen bonded cocrystals were obtained by using 1,4-diiodobenzene (DIB), 1,4-diiodotetrafluorobenzene (DIFB), and iodopentafluorobenzene (IPFB) as XB donors and PTP as acceptor. The structures of the cocrystals showed some XB selectivity between the S and N donors in PTP. However, the limited contribution of XB to the overall molecular packing in these three cocrystals and the results from DSC measu…
Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes
2019
A detailed study of the strong N−X⋯−O−N+ (X = I, Br) halogen bonding interactions in solution and in the solid‐state reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). Density Functional Theory (DFT) calculations were used to investigate the X···O halogen bond (XB) interaction energies in 54 complexes. The XB interaction energies were found to vary from –47.5 to –120.3 kJ mol–1, with the strongest N−I⋯−O−N+ XBs approaching those of 3‐center‐4‐electron [N–I–N]+ halogen‐bonded systems (∼160 kJ mol–1). Using a subset of 32 complexes, stabilized only through N−X···−O−N+ XB interactions, a simplified, computationally fast, electrostatic model to predict the X…