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Atoms and molecules interact with each other through intermolecular forces. These electrostatic forces arise from attractive or repulsive interactions between particles with permanent, partial, or temporary charges. The intermolecular forces between neutral atoms and molecules are ion–dipole, dipole–dipole, and dispersion forces, collectively known as van der Waals forces.
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The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without energy from some external source.
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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
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Dispersive interactions in solution complexes.

Hans-Jörg Schneider1

  • 1FR Organische Chemie, Universität des Saarlandes, D-66041 Saarbrücken, Germany.

Accounts of Chemical Research
|June 18, 2015
PubMed
Summary

Dispersive interactions are crucial for molecular associations in solution, distinct from hydrophobic effects. This study quantifies binding contributions of organic groups, revealing additive effects and the significant role of polarizability in host-guest complexation.

Area of Science:

  • Supramolecular Chemistry
  • Physical Chemistry
  • Chemical Physics

Background:

  • Dispersive interactions are vital in molecular associations but their role in solution has been debated.
  • Separating dispersive and hydrophobic effects in aqueous solutions is challenging due to low polarizability of water.
  • Porphyrin-based systems offer a platform to differentiate these forces.

Purpose of the Study:

  • To discriminate between dispersive and hydrophobic interactions in molecular complexation in aqueous media.
  • To quantify additive binding free energy increments (ΔΔG) for various organic functional groups.
  • To elucidate the influence of polarizability and substrate structure on host-guest complex stability.

Main Methods:

  • Analysis of complexes formed between porphyrins and systematically varied substrates in water.

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  • Measurement of binding free energy increments (ΔΔG) for diverse organic residues.
  • Systematic variation of halogen substituents in host-guest complexes across different media.

    • Main Results:

    • Hydrophobic effects are negligible for complexations with flat surfaces like porphyrins, allowing for dispersive force analysis.
    • Additive binding free energy increments (ΔΔG) were obtained for numerous organic groups, with values increasing with polarizability (e.g., nitro, pyridine).
    • Complex stability with halogenated derivatives consistently increases from fluorine to iodine, correlating with polarizability and indicating dominant dispersive forces.

    Conclusions:

    • Dispersive interactions are significant drivers of molecular complexation in solution, separable from hydrophobic effects.
    • The study provides a quantitative framework for understanding additive contributions of functional groups to binding affinity.
    • Polarizability is a key factor governing dispersive forces in host-guest chemistry, relevant across various systems including proteins.