Halogen Bonding in Iodo-perfluoroalkane/Pyridine Mixtures
- 2 December 2009
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry A
- Vol. 113 (51), 14052-14059
- https://doi.org/10.1021/jp9057127
Abstract
Mole fraction and temperature studies of halogen bonding between 1-iodo-perfluorobutane, 1-iodo-perfluorohexane, 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.Keywords
This publication has 75 references indexed in Scilit:
- Halogenated Benzenes Bound within a Non-polar Cavity in T4 Lysozyme Provide Examples of I⋯S and I⋯Se Halogen-bondingJournal of Molecular Biology, 2009
- σ-hole bonding: molecules containing group VI atomsJournal of Molecular Modeling, 2007
- Directing macromolecular conformation through halogen bondsProceedings of the National Academy of Sciences of the United States of America, 2007
- Halogen bonding: the σ-holeJournal of Molecular Modeling, 2006
- Perfluorocarbon-hydrocarbons self-assembly: halogen bonding mediated intermolecular recognitionJournal of Fluorine Chemistry, 2004
- Perfluorocarbon–hydrocarbon self-assembly: Part 16. 19F NMR study of the halogen bonding between halo-perfluorocarbons and heteroatom containing hydrocarbonsJournal of Fluorine Chemistry, 2002
- Study of polarization CRS and polarization ICRS with application to benzenaJournal of Raman Spectroscopy, 1995
- Interferometric coherent Raman spectroscopy with incoherent light: Some applicationsApplied Physics B Laser and Optics, 1994
- Vibrational dephasing times of bis(dimethylamino)heptamethine iodide determined by CARS using incoherent lightJournal of Raman Spectroscopy, 1994
- Study of the pyridine–methanol system using four‐channel Raman spectroscopy: Concentration dependence of frequencies, line widths and integrated intensitiesJournal of Raman Spectroscopy, 1993