The Geometry and Nature of C─I···O─N Interactions in Perfluoroiodobenzene‐Pyridine <i>N</i>‐oxide Halogen‐Bonded Complexes
Rautiainen, J. M., Valkonen, A., Lundell, J., Rissanen, K., & Puttreddy, R. (2024). The Geometry and Nature of C─I···O─N Interactions in Perfluoroiodobenzene‐Pyridine N‐oxide Halogen‐Bonded Complexes. Advanced Science, Early online. https://doi.org/10.1002/advs.202403945
Julkaistu sarjassa
Advanced SciencePäivämäärä
2024Tekijänoikeudet
© 2024 the Authors
The N─Oxide oxygen in the 111 C─I···⁻O─N+ halogen bond (XB) complexes, formed by five perfluoroiodobenzene XB donors and 32 pyridine N-oxides (PyNO) XB acceptors, exhibits three XB modes: bidentate, tridentate, and monodentate. Their C─I···O XB angles range from 148° to 180°, reflecting the iodine σ-hole's structure-guiding influence. The I···⁻O─N+ angles range from 87° to 152°. On the contrary, the I···⁻O─N+ angles have a narrower range from 107° to 125° in stronger monodentate N─I···⁻O─N+ XBs of N-iodoimides and PyNOs. The C─I···⁻O─N+ systems exhibit a larger variation in I···⁻O─N+ angles due to weaker XB donor perfluoroiodoaromatics forming weak I···O XBs, which allows wider access to electron-rich N-O group regions. Density Functional Theory analysis shows that I···O interactions are attractive even when the I···⁻O─N+ angle is ≈80°. Correlation analysis of structural parameters showed that weak I···O XBs in perfluoroiodobenzene-PyNO complexes affect the C─I bond via n(O)→σ*(C─I) donation less than the N─I bond via n(O)→σ*(N─I) donation in very strong I···O XBs of N-iodoimide-PyNO complexes. This implies that PyNOs' oxygen self-tunes its XB acceptor property, dependent on the XB donor σ-hole strength affecting the bonding denticity, geometry, and interaction energies.
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WileyISSN Hae Julkaisufoorumista
2198-3844Asiasanat
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https://converis.jyu.fi/converis/portal/detail/Publication/220714425
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The authors gratefully acknowledge financial support from the Academy of Finland [grant numbers 351121 (K.R.), 332023 (J.L.), and 338733 (J.M.R.)] for funding.Lisenssi
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