Halogen-bonded cocrystallization with phosphorus, arsenic and antimony acceptors

Research output: Contribution to journalArticlepeer-review


  • Katarina Lisac
  • Filip Topić
  • Mihails Arhangelskis
  • Sara Cepić
  • Patrick A. Julien
  • Christopher W. Nickels
  • Tomislav Friščić
  • Dominik Cinčić

Colleges, School and Institutes


The formation of non-covalent directional interactions, such as hydrogen or halogen bonds, is a central concept of materials design, which hinges on using small compact atoms of the 2nd period, notably nitrogen and oxygen, as acceptors. Heavier atoms are much less prominent in that context, and mostly limited to sulfur. Here, we report the experimental observation and theoretical study of halogen bonds to phosphorus, arsenic and antimony in the solid state. Combining 1,3,5-trifluoro-2,4,6-triiodobenzene with triphenylphosphine, -arsine, and -stibine provides cocrystals based on I···P, I···As and I···Sb halogen bonds. The demonstration that increasingly metallic pnictogens form halogen bonds sufficiently strong to enable cocrystal formation is an advance in supramolecular chemistry which opens up opportunities in materials science, as shown by colossal thermal expansion of the cocrystal involving I···Sb halogen bonds.


Original languageEnglish
Article number61
JournalNature Communications
Issue number1
Publication statusPublished - 4 Jan 2019