Orientation of the Azobenzene Spacer of Carboxylic Methyl Ester Gemini Surfactants in Langmuir Monolayer

Abstract The Langmuir monolayer of carboxylic methyl ester Gemini surfactants with the azobenzene spacer, referred to as MCm(azo)MCm, was prepared and the π‐A isotherms were measured. The result revealed an orientational picture of the azobenzene spacer at the air/water interface. Before irradiation, the planar trans‐azobenzene group adopted an approximate configuration parallel to the interface and lay on the air/water interface. After UV‐light irradiation, the spacer became the twisted cis‐one. Because of the location of the polar headgroups at the air/water interface, the two phenyl rings were also forced to take a near‐parallel orientation with the interface to reduce the free energy. As a result, the spacer thin‐layer was "thickened", which caused an elevation in collapse pressure.