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Effects of microhydration on the characteristics of cation–phenol complexes

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Abstract

The properties of complexes formed by phenol and K+, Na+, Li+ and Mg2+ in the presence of up to four water molecules have been studied by means of computational methods. The interaction becomes stronger as the size of the cation decreases, showing almost no preference between coordinating to the aromatic ring or to the hydroxyl oxygen. As water molecules are introduced, a variety of stable structures arise, where water molecules establish hydrogen bonds among themselves and with the hydroxyl group of phenol. For the most polarizing cations, the strong cation···water interaction gives most stable minima corresponding to arrangements with water molecules and phenol coordinated directly to the cation, with no significant hydrogen bonds among them. However, in Na+ complexes and especially in K+ ones, the interaction with the cation is weaker, so hydrogen bond formation starts to be competitive as more water molecules are included, the most stable minima corresponding to structures where not all water molecules or phenol are directly bound to the cation. This behavior is also reflected on the predicted vibrational spectra, which agree with those determined experimentally. Up to three water molecules, only for K+ and to a less extent Na+, stable minima are found showing red-shifted O–H stretching bands corresponding to water···water and water···phenol hydrogen bonds. With four water molecules, at least one water molecule is located in a second solvation shell, all cations exhibiting red-shifted bands.

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Acknowledgments

The authors thank the financial support from the Ministerio de Ciencia e Innovación and the ERDF 2007–2013 (Grant No. CTQ2009-12524). We are also thankful to the Centro de Supercomputación de Galicia (CESGA) for the use of their computers.

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  1. Departamento de Química Física, Facultade de Ciencias, Universidade de Santiago de Compostela, Campus de Lugo. Avda. Alfonso X El Sabio s/n, 27002, Lugo, Spain

    Alba Campo-Cacharrón & Enrique M. Cabaleiro-Lago

  2. Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CIQUS), Universidade de Santiago de Compostela, Rúa Jenaro de la Fuente, s/n, 15782, Santiago de Compostela, Spain

    Jesús Rodríguez-Otero

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  1. Alba Campo-Cacharrón
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Correspondence to Enrique M. Cabaleiro-Lago.

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Campo-Cacharrón, A., Cabaleiro-Lago, E.M. & Rodríguez-Otero, J. Effects of microhydration on the characteristics of cation–phenol complexes. Theor Chem Acc 131, 1290 (2012). https://doi.org/10.1007/s00214-012-1290-z

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