Halogen bonding in iodo-perfluoroalkane/pyridine mixtures

Haiyan Fan, Jeffrey K. Eliason, C. Diane Moliva A., Jason L. Olson, Scott M. Flancher, M. W. Gealy, Darin J. Ulness

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Abstract

Mole fraction and temperature studies of halogen bonding between 1-iodo-perfluorobutane, 1-iodoperfluorohexane, or 2-iodo-perfluoropropane and pyridine were performed using noisy light-based coherent anti-Stokes Raman scattering (I(2) CARS) spectroscopy. The ring breathing mode of pyridine both is highly sensitive to halogen bonding and provides a strong I(2) CARS signal. As the lone pair electrons from the pyridinyl nitrogen interact with the σ-hole on the iodine from the iodo-perfluoroalkane, the ring breathing mode of pyridine blue-shifts proportionately with the strength of the interaction. The measured blue shift for halogen bonding of pyridine and all three iodo-perfluoroalkanes is comparable to that for hydrogen bonding between pyridine and water. 2-Iodo-perfluoropropane displays thermodynamic behavior that is different from that of the 1-iodo-perfluoroalkanes, which suggests a fundamental difference at the molecular level. A potential explanation of this difference is offered and discussed.

Original languageEnglish
Pages (from-to)14052-14059
Number of pages8
JournalJournal of Physical Chemistry A
Volume113
Issue number51
DOIs
Publication statusPublished - Dec 24 2009

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fan, H., Eliason, J. K., Diane Moliva A., C., Olson, J. L., Flancher, S. M., Gealy, M. W., & Ulness, D. J. (2009). Halogen bonding in iodo-perfluoroalkane/pyridine mixtures. Journal of Physical Chemistry A, 113(51), 14052-14059. https://doi.org/10.1021/jp9057127