Light-induced self-assembly and decay of J aggregates of thiamonomethinecyanine dyes

Abstract

Formation of J aggregates, that is, one-dimensional supramolecular self-organizations in which the transition moments of individual molecules are aligned parallel to the line joining their centers through a "head-to-tail" arrangement, normally proceed via electrostatic interactions between oppositely charged molecular groups; this is facilitated by an electrolyte medium. Here, we show that J aggregates of thiamonomethinecyanine dyes in a solution can be assembled from dye dimers by illuminating the solution with light of the appropriate wavelength to induce excitation of the dye dimers. The reverse process is also demonstrated by application of light of the correct wavelength to induce excitation of the J aggregates. Our results indicate that spontaneous J aggregation in the dark and formation of J aggregates through illumination proceed through different mechanisms; the former resulting in an increase in the number of the aggregates and the latter in an increase in the size of the aggregates.

Keywords: aggregation; dimers; dyes/pigments; dynamic equilibrium; photoexcitation.