Halogen-bonded cocrystallization with phosphorus, arsenic and antimony acceptors

Katarina Lisac, Filip Topić, Mihails Arhangelskis, Sara Cepić, Patrick A. Julien, Christopher W. Nickels, Andrew J. Morris, Tomislav Friščić () and Dominik Cinčić ()
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Katarina Lisac: University of Zagreb
Filip Topić: McGill University
Mihails Arhangelskis: McGill University
Sara Cepić: University of Zagreb
Patrick A. Julien: McGill University
Christopher W. Nickels: McGill University
Andrew J. Morris: University of Birmingham, Edgbaston
Tomislav Friščić: McGill University
Dominik Cinčić: University of Zagreb

Nature Communications, 2019, vol. 10, issue 1, 1-10

Abstract: Abstract 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.

Date: 2019
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DOI: 10.1038/s41467-018-07957-6

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