Gemini-like Molecular Clips and Tweezers: The Influence of Structure and Guest Binding on Interfacial Tension

Abstract

In a series of experiments, we studied the interfacial activity of aromatic aliphatic molecules with rigid gemini-like structures at the interface between toluene and water. These molecules, called clips and tweezers, have rigid central benzene or naphthalene spacer-units, each substituted with two polar groups as well as two rigid aromatic side walls. They can serve as host molecules and selectively bind a variety of electron-deficient aromatic and aliphatic guest molecules. In different experiments, we compared the interfacial tensions with the calculated hydrophilic-lipid-balance (HLB) values of these molecules. The measured interfacial tensions depend as much on the HLB values as on the geometric structure of the water insoluble molecules. The concentration dependence of the surface tension gave evidence for the formation of inverse micellar aggregates, which were formed in the oil phase above a well-defined value of the bulk concentration. The presence of aggregates in the organic liquid could also be investigated by dynamic light scattering measurements. We observed typical diameters of the inverse micellar aggregates in the order of 5.6 nm, and the critical micelle concentrations (cmc's) coincided well with the results of interfacial tension measurements. From the surface excess in the vicinity of the cmc, we calculated the space occupied by a single clip molecule on the self-assembled monolayer. The observed molecular surface area was in agreement with the effective molecular diameters of the molecules. In additional experiments, we could also show that complexes with aromatic guest molecules such as 1,2-4,5-tetracyanobenzene (TCNB) led to a reduction of the amphiphilic clip properties.