Two-Dimensional Aggregation of a Long-Chain Thiacarbocyanine Dye Monolayer on Polyanion Subphases

Two-dimensional aggregation of a long-chain thiacarbocyanine dye 5,5‘-dichloro-3,3‘-dioctadecyl-9-ethylthiacarbocyanine perchlorate in the monolayers on subphases containing different synthetic polyanions were studied. The aggregation process of the dye in the monolayers was followed by the in situ measurement of the absorption spectra of the monolayers. Two J aggregates were observed at 648 and 666 nm in the monolayer on a plain water surface at all the surface pressures. On the subphase containing poly(acrylic acid), sodium (PAA), and poly(vinyl sulfonic acid), potassium salt (PVS) subphases, the J aggregates were formed at relative high surface pressures (15 and 17.5 mN/m, respectively). On the PVS subphase, an H aggregate at 472 nm was also observed at higher surface pressure (>40 mN/m). On the poly(styrenesulfonic acid), sodium salt (PSS) subphase, neither J nor H aggregates were observed even at higher surface pressures. Models were proposed to explain these interactions between the positively charged dye monolayers and polyanions.