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Probing covalency in halogen bonds through donor K-edge X-ray absorption spectroscopy: polyhalides as coordination complexes

TitleProbing covalency in halogen bonds through donor K-edge X-ray absorption spectroscopy: polyhalides as coordination complexes
Publication TypeJournal Article
Year of Publication2017
AuthorsMustoe, CL, Gunabalasingam, M, Yu, D, Patrick, BO, Kennepohl, P
JournalFaraday Discuss.
Volume203
Pagination79-91
Type of Articlearticle
KeywordsHalogen Bonding, X-ray absorption spectroscopy
Abstract

The properties of halogen bonds (XBs) in solid-state I 2 X − and I 4 X − materials (where X = Cl, Br) are explored using donor K-edge X-ray absorption spectroscopy (XAS) to experimentally determine the degree of charge transfer in such XB interactions. The degree of covalency in these bonds is substantial, even in cases where significantly weaker secondary interactions are observed. These data, in concert with previous work in this area, suggests that certain halogen bonds have covalent contributions to bonding that are similar to, and even exceed, those observed in transition metal coordinate bonds. For this reason, we suggest that XB interactions of this type be denoted in a similar way to coordination bonds (X → Y) as opposed to using a representation that is the same as for significantly less covalent hydrogen bonds (X⋯Y).