Effects of Hydrogen Bonding on the Monolayer Properties of Amphiphilic Double-Decker-Shaped Polyhedral Silsesquioxanes

Abstract

"Core-corona" type amphiphiles, which comprise double-decker-shaped POSSs (DDSQs) as the core and two or four di(ethylene glycol) (DEG) units as the coronae, have recently been reported to form a stable monolayer at the air-water interface. In this paper, another core-corona amphiphile, 2DEGNH-DDSQ, which has a urethane group at the end of the coronae, was synthesized to elucidate the effects of hydrogen bonding on monolayer properties. The surface pressure-area isotherm and Brewster angle microscopy revealed that 2DEGNH-DDSQ initially formed rodlike assemblies. They subsequently coalescence to form a uniform monolayer with compression. Actually, 2DEGNH-DDSQs are well ordered in the rodlike assembly because of the strong hydrogen bonds among the urethane groups, as confirmed by FT-IR spectra. Although the monolayer was not transferred onto a solid substrate, mixing of 2DEGNH-DDSQ with 2DEG-DDSQ, which has already been reported to form a liquidlike monolayer, overcame this problem. The 1:1 molar mixture of 2DEGNH-DDSQ and 2DEG-DDSQ forms a uniform liquidlike monolayer. The mixed monolayer was transferred onto a solid substrate as a Z-type Langmuir-Blodgett film. Atomic force microscopic (AFM) images of the mixed-bilayer film showed a uniform surface with root-mean-square surface roughness of 0.21 nm. The intermolecular hydrogen bonds between the urethane groups in 2DEGNH-DDSQ and the hydroxyl groups in 2DEG-DDSQ improve the monolayer properties, which enable successful transfer of the LB film.