Stable, ordered multilayers of partially fluorinated bolaamphiphiles at the air–water interface

ABSTRACT The article presents systematic research on Langmuir films of partially fluorinated bolaamphiphiles of different shapes. Such films exhibit a layering transition from a monolayer to a trilayer during compression on the air–water interface. Further compression gives different results depending on the shape and degree of fluorination of the molecules. Partially fluorinated compounds form well defined multilayers in a reversible process. The balance between rigidity and flexibility of the molecules, adjusted by the fluorination and shape of the molecules, seems to be the key factor in avoiding irreversible aggregation of the molecules and creating ordered multilayer structures. Anchor-shaped bolaamphiphiles form a trilayer and, subsequently, a 9-layer film due to a double roll-over mechanism. In contrast, when trilayer films of X-shaped bolaamphiphiles are compressed, 5- and 7-layer films are created according to a different mechanism. Films of thickness of up to nine layers were transferred from the water surface to solid substrates in a single step procedure without any distortion in the structure of the layers. X-ray reflectometry (XRR) was used to measure the thickness of the layers. Perfect fits of the XRR data to theoretical equations allowed for a conclusion that the multilayers are well-ordered lamellar structures. These investigations lead to an improvement in the general understanding of trilayer and multilayer formation and indicate that only in exceptional cases it happens due to a roll-over process.