A1 Journal article (refereed)
Inherently Unstable Carbonyl Hypoiodites as Extremely Strong Neutral Halogen Bond Donors (2021)

Rissanen, K., Yu, S., Truong, K.-N., & Ward, J. S. (2021). Inherently Unstable Carbonyl Hypoiodites as Extremely Strong Neutral Halogen Bond Donors. Angewandte Chemie, Early online. https://doi.org/10.1002/anie.202108126

JYU authors or editors

Publication details

All authors or editors: Rissanen, Kari; Yu, Shilin; Truong, Khai-Nghi; Ward, Jas S.

Journal or series: Angewandte Chemie

ISSN: 1433-7851

eISSN: 1521-3773

Publication year: 2021

Volume: Early online

Publisher: Wiley

Publication country: Germany

Publication language: English

DOI: https://doi.org/10.1002/anie.202108126

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/77193


A series of neutral halogen-bonded O–I–N complexes were prepared from in-situ formed carbonyl hypoiodites and aromatic organic bases (pyridine, DMAP, 4-morpholinopyridine and 4-piperidinopyridine). The carbonyl hypoiodites exhibit a very strongly polarized iodine atom with larger s -holes than any known uncharged halogen bond donor. The hypoiodite synthesized from trifluoroacetic acid has a s -hole of +234.55 kJ/mol, which surpasses the previously strongest XB donor N -iodosaccharin that had a value of +226.36 kJ/mol. Modulating the Lewis basicity of the selected pyridine derivatives and carboxylates leads to halogen-bonded complexes where the classical O‒I···N halogen bond transforms more into a halogen-bonded COO – ···I – N + ion-pair (salt) with a strongly asymmetric O – I – N moiety. Detailed single crystal X-ray analyses, 1 H- 15 N HMBC NMR studies, and DFT calculations reveal the halogen bonding geometries of the carbonyl hypoiodite-based O – I – N complexes, confirming that in the solid-state the iodine atom is located much closer to the N-atom of the pyridine derivatives than its original position at the carboxylate O-atom.

Keywords: halogens; chemical bonds; supramolecular chemistry

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Last updated on 2021-20-07 at 10:39