Interfacial organization of Y-shaped rod-coil molecules packed into cylindrical nanoarchitectures

The behavior at the air/water interface and the structures of Longmuir-Blodgett monolayers at different surface pressures of rod-coil molecules, which consist of a Y-shaped rigid aromatic segment containing peripheral tetradecyloxy groups and a flexible poly(ethylene oxide) (PEO) chain with 17, 21, 34, or 45 repeating ethylene oxide units (Y17, Y21, Y34, and Y45), were investigated. For the Y21 and Y34 molecules, AFM images revealed two kinds of cylindrical nanoarchitectures formed upon compression. The nanostructured films were further investigated by UV/Vis and FTIR spectroscopy. The formation of the cylindrical nanoarchitectures was due to different tilting angles offered by the mismatch of the cross-sectional areas of the PEO chain and the benzene ring with attached alkyl chains, and the different PEO contents of the molecules. The multiple pi,pi stacking and hydrophobic interactions provide exceptional stability of the nanostructures and allow them to be preserved in the course of flipping. For the shortest PEO chain of the Y17 molecule, spontaneous aggregation occurred. The Y45 molecule revealed the formation of 2D circular domains caused by entanglement of the longest PEO chains and coiling at the air/water interface. In addition, an interesting vortical morphology was obtained for the Y21 molecule upon deposition of the film onto a mica substrate, which indicates that the substrate chemistry also has an effect on the morphologies during the film-transfer process.