A Long-Lived Halogen-Bonding Anion Triple Helicate Accommodates Rapid Guest Exchange

Casey J. Massena, Daniel A. Decato, Orion B. Berryman

Research output: Contribution to journalArticlepeer-review

31 Scopus citations


Anion-templated helical structures are emerging as a dynamic and tractable class of supramolecules that exhibit anion-switchable self-assembly. We present the first kinetic studies of an anion helicate by utilizing halogen-bonding m-arylene-ethynylene oligomers. These ligands formed high-fidelity triple helicates in solution with surprisingly long lifetimes on the order of seconds even at elevated temperatures. We propose an associative ligand-exchange mechanism that proceeded slowly on the same timescale. In contrast, intrachannel anion exchange occurred rapidly within milliseconds or faster as determined by stopped-flow visible spectroscopy. Additionally, the helicate accommodated bromide in solution and the solid state, while the thermodynamic stability of the triplex favored larger halide ions (bromide≈iodide≫chloride). Taken together, we elucidate a new class of kinetically stable helicates. These anion-switchable triplexes maintain their architectures while accommodating fast intrachannel guest exchange.

Original languageEnglish
Pages (from-to)16109-16113
Number of pages5
JournalAngewandte Chemie - International Edition
Issue number49
StatePublished - Dec 3 2018


  • halogen bonding
  • helical structures
  • host-guest systems
  • kinetics
  • supramolecular chemistry


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