Mechanism of rhodamine 6G molecular aggregation in montmorillonite colloid

Stopped-flow mixing device and visible absorption spectroscopy were used for the analysis of dye rhodamine 6G (R6G) molecular aggregation in the colloids based on Na-saturated montmorillonite. Two stages of the reaction were identified: The first stage was very short and taking only several seconds, involving the adsorption of R6G cations and their initial aggregation on the surface of colloid particles. The initially formed J-aggregates exhibited similar spectral properties as monomeric form of R6G. In the second stage, initially formed aggregates converted to sandwich-type H-aggregates absorbing light at significantly lower wavelengths and adsorbed monomers. The aggregate rearrangement took several hours. Monomers, with the spectral properties identical to R6G solution, were also identified as a component in complex spectra using principal component analysis (PCA) and multivariate curve resolution (MCR). Partial bleaching of the dye was also proven. Reaction kinetics of the rearrangement of the aggregates followed the model considering a complex mechanism of the molecular aggregation. Data fits using stretched-exponential function led to the determination of rate constants, which had been in the range 10^?3?4×10^?3s^?1.