Diphenylacetylene (tolan) derivatives with self-complementary aryl halides and halogen bond-accepting nitriles form 2D bricklayer packing motifs when halogen bonding occurs. When halogen bonding is absent, as occurred with fluorinated aryl bromides, the molecules adopt other packing motifs. These results suggest halogen bonding is potentially useful for producing rarely observed 2D bricklayer m...

Aryl-bromine bonds are successfully cleaved by cobalt(II) porphyrins in basic media to give Co(por)Ar (por = porphyrin) in good yields. Mechanistic studies suggested that the aryl-bromine bond is cleaved through a halogen atom transfer mechanism, which is different from the aryl-halogen bond cleavage mechanism with other group 9 metalloporphyrins.

We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyridine)iodine](+) and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine](+) BF4(-) complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. T...

The competition between hydrogen- and halogen-bonding interactions in complexes of 5-halogenated 1-methyluracil (XmU; X = F, Cl, Br, I, or At) with one or two water molecules in the binding region between C5-X and C4=O4 is investigated with M06-2X/6-31+G(d). In the singly-hydrated systems, the water molecule forms a hydrogen bond with C4=O4 for all halogens, whereas structures with a halogen bo...

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals forme...

MP2/aug'-cc-pVTZ calculations have been carried out to investigate the halogen-bonded complexes formed when CO and CS act as electron-pair donors through C to ClF, ClNC, ClCl, ClOH, ClCN, ClCCH, and ClNH₂. CO forms only complexes stabilized by traditional halogen bonds, and all ClY molecules form traditional halogen-bonded complexes with SC, except ClF which forms only an ion-pair complex. Ion-...

MP2/aug-cc-pVTZ calculations were performed for complexes of BrF₃ and BrF₅ acting as Lewis acids through the bromine centre, with species playing a role of Lewis base: dihydrogen, acetylene, ethylene, and benzene. The molecular hydrogen donates electrons by its σ-bond, while in remaining moieties-in complexes of hydrocarbons; such an electron transfer follows from π-electrons. The complexes are...

Halogen bond has attracted a great deal of attention in the past years for hit-to-lead-to-candidate optimization aiming at improving drug-target binding affinity. In general, heavy organohalogens (i.e., organochlorines, organobromines, and organoiodines) are capable of forming halogen bonds while organofluorines are not. In order to explore the possible roles that halogen bonds could play beyon...

The crystallization of a 1:1 molar solution of 1,2-di-iodo-3,4,5,6-tetra-fluoro-benzene (o-DITFB) and tetra-butyl-ammonium bromide (n-Bu4NBr) from di-chloro-methane yielded pure white crystals of a halogen-bonded compound, C16H36N(+)·Br(-)·C6F4I2·0.5CH2Cl2 or [(n-Bu4NBr)(o-DITFB)]·0.5CH2Cl2. The compound may be described as a quaternary system and may be classified as a salt-cocrystal solvate. ...