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Fluorine-fluorine interactions in the solid state: an experimental and theoretical study.

Robert J Baker1, Paula E Colavita, Deirdre M Murphy

  • 1School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland. bakerrj@tcd.ie

The Journal of Physical Chemistry. A
|November 29, 2011
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This study reveals weak stabilizing interactions between perfluorinated chains, confirmed by computational chemistry. These interactions are key for physisorption onto perfluorinated surfaces, enabling new material applications.

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Area of Science:

  • Solid-state chemistry
  • Computational chemistry
  • Materials science

Background:

  • Perfluorinated compounds exhibit unique intermolecular interactions.
  • Understanding these interactions is crucial for designing advanced materials and surface modifications.

Purpose of the Study:

  • To investigate and characterize weak C-F···F-C and C-F···H-C interactions in solid-state perfluorinated compounds.
  • To computationally assess the energetic contribution of these interactions.
  • To explore the application of these interactions in surface physisorption.

Main Methods:

  • Comparison of solid-state structures of three perfluorinated compounds.
  • Comprehensive computational chemistry investigation, including Atoms-in-Molecules (AIM) study.
  • Characterization of physisorption using Infrared Reflection Absorption Spectroscopy (IRRAS).

Main Results:

  • Identification of C-F···F-C and C-F···H-C interactions closer than van der Waals radii.
  • Computational analysis revealed stabilizing energies ranging from 0.26 to 29.64 kcal/mol.
  • AIM study confirmed the presence and non-packing origin of specific C-F···F-C interactions.
  • Successful physisorption of perfluorinated compounds onto a perfluorinated monolayer was demonstrated.

Conclusions:

  • Weak C-F···F-C and C-F···H-C interactions play a significant role in the solid-state structures of perfluorinated compounds.
  • These interactions are quantifiable and contribute to molecular stabilization.
  • The findings enable the rational design of surface functionalization and physisorption processes using perfluorinated materials.