Anion-π Interactions in Monolayers Formed by Amphiphilic Electron-Deficient Aromatic Compounds at Air/Water Interfaces.

Biological systems precisely and selectively control ion binding through various chemical reactions, molecular recognition, and transport by virtue of effective molecular interactions with biological membranes and proteins. Because ion binding is inhibited in highly polar media, recognition systems for anions in aqueous media, which are relevant to biological and environmental systems, are still limited. In this study, we explored the anion binding of Langmuir monolayers formed by amphiphilic naphthalenediimide (NDI) derivatives with a series of substituents at air/water interfaces via anion-π interactions. Density functional theory (DFT) simulations revealed that the binding of anions originating from anion-π interactions is related to the electron density of the anions. At the air/water interfaces, amphiphilic NDI derivatives formed Langmuir monolayers, and the addition of anions caused expansion of the Langmuir monolayers. The anions with larger hydration energies related to electron density showed larger binding constants (Ka) for 1:1 stoichiometry with the NDI derivatives. The loosely packed monolayer formed by the amphiphilic NDI derivatives with bromine groups showed a better anion response. In contrast, the binding of NO3- was significantly enhanced in the highly packed monolayer. These results indicate that the packing of NDI derivatives with rigid aromatic rings influenced the binding of the anions. These results provide insight into ion binding using the air/water interface as a promising recognition site for mimicking biological membranes. In future, sensing devices can be developed using Langmuir-Blodgett films on electrodes. Furthermore, the capture of anions on electron-deficient aromatic compounds can lead to doping or composition technologies for n-type semiconductors.

Anion-π interaction at the solid/water interfaces.

Anion-π interaction has been found to play a key role in interfacial phenomena. In this study, we evaluated the anion-π interactions at the solid/water interface. Anion adsorption originating from anion-π interaction at the interfaces followed the hydration energy and the presence of conjugated systems of the anions by the QCM measurements. Force curve measurements revealed that the single-molecule force of anion-π interaction between an NDI unit and the negatively charged surface of the cantilever was ∼40 pN. To the best of our knowledge, this is the first example of obtaining a single-molecule force for anion-π interactions.