Spacer-controlled aggregation and surface morphology of a selenacarbocyanine dye on gemini monolayers

The adsorption and aggregation of a selenacarbocyanine dye (3,3-disulfopropyl-9-methyl-selenacarbocyanine, SeCy) onto Langmuir monolayers of a series of gemini amphiphiles with different methylene spacers were investigated. When the monolayers of the gemini amphiphiles were spread on the dye-containing subphase, the dye could be easily adsorbed and aggregated onto the monolayers through the electrostatic and pi-pi interaction. The dye formed complexes with gemini amphiphiles and stacked as J-aggregates in all the transferred multilayers, regardless of the structure of gemini amphiphiles. However, the surface morphologies of the complex monolayers showed a significant dependence on the spacer length of the gemini amphiphiles and the temperature of the subphase. Nanorods were observed for the complex films with spacer lengths ranged from 4 to 10 methylenes. With the temperature of the subphases increased from 20 degrees C to 30 degrees C, aligned longer nanofibers were formed instead. Although both the gemini amphiphiles and the dye were achiral, strong circular dichroism (CD) signals were observed for the transferred complex films. However, the CD signals could be just opposite in different places of the transferred films, suggesting that a resolved enantiomeric micro/nanostructure coexisted in the films. On the other hand, for the complex film of the dye with the gemini amphiphile of two methylenes spacer, neither CD signal nor ordered surface morphologies were detected in any place of the film although the dye itself stilled formed J-aggregate in the film. It was suggested that regular nanoarchitectures and resolved chiral domains could be observed only when the spacer of gemini amphiphiles is comparative to the distance between the two SO3- groups in the dye.