Halogen bonding

Halogen bonding is the attractive, non-covalent interaction that can form between an electrophilic region of a halogen atom in a molecule and a nucleophilic region of a molecule. The bonding can be exploited in areas such as supramolecular chemistry, crystal engineering and the fabrication of liquid crystals.

Latest Research and Reviews

  • Research |

    Halogen-bonded co-crystals of a fluorinated azobenzene derivative and a volatile co-former can be cut, carved or engraved with micrometre-scale precision using low-power visible light. The proposed mechanism involves the local evaporation of the volatile component followed by recrystallization of the azobenzene co-former near the edge of the irradiation area.

    • T. H. Borchers
    • , F. Topić
    •  & C. J. Barrett
    Nature Chemistry 14, 574-581
  • Research |

    Organogel formation was observed immediately during the addition of diisocyanate to a solution of para-substituted bis(3-aminopropyl)hexaisobutyl-substituted cage octasilsesquioxane (T8 cage) monomer at room temperature when above the critical gel concentrations (Cgs). T8-polyureas with phenylurea moieties promoted organogel formation in comparison with T8-polyureas with nonphenylurea moieties. The substitution of methyl groups at the ortho position of the phenylurea groups provided lower Cgs. Increasing the intermolecular interaction between the ureido groups in the T8-polyurea enhanced organogel formation, which was supported by the FT-IR analysis of the dried gels.

    • Tasuku Kamitani
    • , Ayano Ishida
    •  & Kensuke Naka
    Polymer Journal 54, 161-167
  • Research
    | Open Access

    Current models of halogen bonding describe the σ-symmetric component of this interaction but do not contemplate the possibility of π-covalency. Here the authors provide experimental and computational evidence of π-covalency in halogen bonds involving radical cation halogen bond donors.

    • Cameron W. Kellett
    • , Pierre Kennepohl
    •  & Curtis P. Berlinguette
  • Research
    | Open Access

    Carbon atoms of various species typically function as acceptors of noncovalent interactions when they are part of a π-system. Here, the authors report their discovery of a noncovalent halogen bond involving the isocyano carbon lone pair, which results in adducts with strongly reduced isocyanide odor.

    • Alexander S. Mikherdov
    • , Alexander S. Novikov
    •  & Vadim Yu. Kukushkin
  • Research
    | Open Access

    Scanning tunnelling microscopy (STM) is commonly used to study 2D molecular self-assembly but is not always enough to fully solve a supramolecular structure. Here, the authors combine a high-resolution version of STM with first-principles simulations to precisely identify halogen bonding in polycyclic aromatic molecules.

    • James Lawrence
    • , Gabriele C. Sosso
    •  & Giovanni Costantini
  • Research
    | Open Access

    Organic heterostructures attract attention in material chemistry but the precise bottom-up synthesis is still challenging. Herein the authors present a hierarchical self-assembly approach to synthesize one-dimensional organic heterostructures by regulating the noncovalent interactions.

    • Ming-Peng Zhuo
    • , Jun-Jie Wu
    •  & Liang-Sheng Liao

News and Comment

  • News & Views |

    Rotaxanes with cyclodextrin end groups have been used as a platform to investigate anion binding in water, revealing that halogen bonding can serve as the basis for molecular recognition in aqueous solvents, which may have implications in medicinal chemistry and beyond.

    • Mark S. Taylor
    Nature Chemistry 6, 1029-1031
  • News & Views |

    Halogen bonding connects a wide range of subjects — from materials science to structural biology, from computation to crystal engineering, and from synthesis to spectroscopy. The 1st International Symposium on Halogen Bonding explored the state of the art in this fast-growing field of research.

    • Mate Erdelyi
    Nature Chemistry 6, 762-764
  • News & Views |

    The behaviour of di-selenol enzyme mimics indicates that a halogen bond between selenium and iodine, and a chalcogen interaction between the two selenium atoms, play an important role in the activation of thyroid hormones.

    • Pierangelo Metrangolo
    •  & Giuseppe Resnati
    Nature Chemistry 4, 437-438