Monolayer effect of a gemini surfactant with a rigid biphenyl spacer on its self-crystallization at the air/liquid interface

Abstract

A gemini surfactant with a biphenyl spacer can spontaneously generate crystals at the air/solution interface. X-ray crystallography reveals that surfactant molecules exhibit an almost fully extended conformation with interdigitating alkyl chains, together with an approximate co-planarity of two C—C—C planes in two alkyl chains of one gemini molecule, and a prominent dihedral angle between the benzene rings and C—C—C planes of the alkyl chains. Infrared reflection–absorption spectroscopy shows that the gemini surfactant was stretched at the air/water interface, with the hydrocarbon chains oriented at a tilt angle of ∼75° with respect to the surface normal. In particular, the biphenyl group is more or less perpendicular to the water surface, and the C—C—C plane of the alkyl chain tends to be parallel to the water surface. Both results point out a remarkable similarity in the molecular conformation between the crystal and the monolayer. Meanwhile, dynamic light scattering and transmission electron microscopy results indicate that the crystallization of such gemini surfactants at the interface is contrary to the crystallization behavior in the bulk phase, meaning that the surfactant solution can only form a supersaturated solution as it is cooled, though the crystallization temperature of 296 K is lower than the Krafft temperature (∼303 K). Therefore, our findings indicate that the Gibbs monolayer of the gemini surfactant plays a critical role in its interfacial crystallization. Additionally, multiple weak intermolecular interactions, involving van der Waals interaction, π–π stacking and cationic–π interactions, as well as the hydrophobic effect during the aggregation of the gemini molecule in solution, are responsible for the formation of the interfacial crystal.