Fluorine鈥揊luorine Interactions in the Solid State: An Experimental and Theoretical Study

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• 作者：Robert J. Baker ; Paula E. Colavita ; Deirdre M. Murphy ; James A. Platts ; John D. Wallis
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：February 9, 2012
• 年：2012
• 卷：116
• 期：5
• 页码：1435-1444
• 全文大小：1082K
• 年卷期：v.116,no.5(February 9, 2012)
• ISSN：1520-5215

文摘

The solid state structures of three compounds that contain a perfluorinated chain, CF₃(CF₂)₅CH₂CH(CH₃)CO₂H, CF₃(CF₂)₅(CH₂)₄(CF₂)₅CF₃ and {CF₃(CF₂)₅CH₂CH₂}₃P鈺怬 have been compared and a number of C鈥揊路路路F鈥揅 and C鈥揊路路路H鈥揅 interactions that are closer than the sum of the van der Waals radii have been identified. These interactions have been probed by a comprehensive computational chemistry investigation and the stabilizing energy between dimeric fragments was found to be 0.26鈥?9.64 kcal/mol, depending on the type of interaction. An Atoms-in-Molecules (AIM) study has confirmed that specific C鈥揊路路路F鈥揅 interactions are indeed present, and are not due simply to crystal packing. The weakly stabilizing nature of these interactions has been utilized in the physisorption of a selected number of compounds containing long chain perfluorinated ponytails onto a perfluorinated self-assembled monolayer, which has been characterized by IRRAS (Infrared Reflection Absorption Spectroscopy).