Summary
Charge-transfer interactions are often assumed to be dominant among the noncovalent interactions that govern the solute retention in electron donor-acceptor chromatography. This popular view, however, has been called into question by recent studies that suggest an important role for electrostatic interactions in the formation of donor-acceptor complexes. We reported here an experimental investigation concerning the question as to whether charge-transfer or electrostatic interactions are the driving force for solute retention in donor-acceptor chromatography. Using three chromatographic systems composed of a dinitrobenzene derived stationary phase and a hexane based mobile phase, we determined retention factors for a range of aliphatic and aromatic hydrocarbons and correlated them with molecular properties that describe the solute's dispersion, charge-transfer, and electrostatic characteristics. It was found that the molecular polarizability and ionization potential give either very poor or no correlation with solute retention whereas the molecular quadrupole moment is a linear function of the logarithmic retention factor. These results were interpreted as showing that electrostatic, rather than charge-transfer or dispersion, interactions play a major role in determining solute retention. The dominance of the electrostatic interactions over the other noncovalent interactions was discussed in terms of distance dependency of the interaction energy.
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Dedicated to Professor John H. Knox on the occasion of his 70th birthday.
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Wan, Q.H., Ramaley, L. & Guy, R. The driving force for solute retention in electron donor-acceptor chromatography: Electrostatic versus charge-transfer interactions. Chromatographia 48, 523–528 (1998). https://doi.org/10.1007/BF02466644
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DOI: https://doi.org/10.1007/BF02466644