Theoretical, Solid-State, and Solution Quantification of the Hydrogen Bond-Enhanced Halogen Bond

Daniel A. Decato, Asia Marie S. Riel, James H. May, Vyacheslav S. Bryantsev, Orion B. Berryman

Research output: Contribution to journalArticlepeer-review

26 Scopus citations


Proximal noncovalent forces are commonplace in natural systems and understanding the consequences of their juxtaposition is critical. This paper experimentally quantifies for the first time a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) without the complexities of protein structure or preorganization. An HBeXB is a halogen bond that has been strengthened when the halogen donor simultaneously accepts a hydrogen bond. Our theoretical studies suggest that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond. Furthermore, stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures of halide complexes (X=Br, I) reveal that HBeXBs produce shorter halogen bonds than non-hydrogen bond analogues. 19F NMR titrations with chloride highlight that the HBeXB analogue exhibits stronger binding. Together, these results form the foundation for future studies concerning hydrogen bonds and halogen bonds in close proximity.

Original languageEnglish
Pages (from-to)3685-3692
Number of pages8
JournalAngewandte Chemie - International Edition
Issue number7
StatePublished - Feb 15 2021


  • bond theory
  • halogen bonds
  • hydrogen bonds
  • noncovalent cooperativity
  • supramolecular chemistry


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