The Surface Chelate Effect

The presence of a surface chelate effect is established in the model system of Cu2+ adsorption on a self-assembled monolayer of 16-mercaptohexadecanoic acid (MHA) on Au. The formation constant of Cu2+ with the MHA surface was found to be 119 ± 3.2 times greater than that of Cu2+ with succinic acid (...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2003-07, Vol.125 (28), p.8454-8455
Main Authors: Major, Ryan C, Zhu, X.-Y
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Solid-liquid interface
Surface physical chemistry
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Summary:The presence of a surface chelate effect is established in the model system of Cu2+ adsorption on a self-assembled monolayer of 16-mercaptohexadecanoic acid (MHA) on Au. The formation constant of Cu2+ with the MHA surface was found to be 119 ± 3.2 times greater than that of Cu2+ with succinic acid (HOOC−(CH2)2−COOH), and 213 ± 4.0 times greater than that of Cu2+ with glutaric acid (HOOC−(CH2)3−COOH) in aqueous solutions. Both of these molecules are known to chelate to metal ions forming seven- and eight-membered rings. The greater surface chelate effect is attributed to the presence of the two-dimensional array of ligands on the surface. We believe the surface chelate effect demonstrated here is of general significance to adsorption on molecular surfaces and should depend strongly on chemical functionality and monolayer structure.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja035544q