Langmuir-Blodgett Monolayers of Cationic Dyes in the Presence and Absence of Clay Mineral Layers: N,N′-Dioctadecyl Thiacyanine, Octadecyl Rhodamine B and Laponite

Langmuir−Blodgett (LB) films of N,N′-dioctadecyl thiacyanine perchlorate (TC18) and octadecyl rhodamine B chloride (RhB18) and their mixtures in the presence and absence of clay mineral layers were investigated by recording surface pressure−area (π−A) isotherms and by UV−vis and fluorescence spectroscopies. The π−A isotherms of TC18, RhB18, and their mixtures are characteristic of liquid expanded state behavior with repulsive interactions between the two cationic dyes. In the presence of laponite, the π−A isotherms show liquid expanded and condensed-state behavior. In laponite dispersions and in monolayers, TC18 has a strong tendency to aggregate with formation of H- and J- aggregates. The absorption and fluorescence maxima of the monomers in the films are at 435 nm and at 480 nm; H-dimers have an absorption maximum around 410 nm and do not fluoresce. J-dimers are present in all the films with absorption maximum at 461 nm and fluorescence at 463 nm. RhB18 is mainly present as monomers in the LB films with an absorption maximum at 576 nm and fluorescence at 595 nm. Fluorescence resonance energy transfer from TC18 to RhB18 has been observed in clay dispersions and in films with and without laponite. The optimum condition for TC18 → RhB18 fluorescence energy transfer in the films is 90 mol % TC18 + 10 mol % RhB18.