Luminescence Properties of the Mixed J-Aggregate of Two Kinds of Cyanine Dyes in Layer-by-Layer Alternate Assemblies

Abstract

The layer-by-layer alternate assemblies incorporating two kinds of cyanine dyes have been fabricated by alternately adsorbing a cationic polyelectrolyte and anionic cyanine dyes on the quartz plate. A thiacyanine dye (dye I) was employed as the donor and two kinds of thiacarbocyanine dye having a meso-alkyl group m -ethyl (dye II), m -methyl (dye III) as the acceptor. The mole fraction of the acceptor in the mixed J-aggregate, χ, was varied from 0 to 1. It is confirmed that these dye combinations form the mixed J-aggregate in the alternate assemblies. From steady-state fluorescence spectra of the molecular assemblies, excitation energy transfer from the donor J-aggregate to the acceptor J-aggregate is observed, whose kinetics obeys the Stern−Volmer relationship. The experimentally determined rate constant of energy transfer, k ET, is fairly large, indicating efficient energy transfer due to exciton migration through the donor J-aggregate. The relative fluorescence quantum yield and the fluorescence lifetime of the acceptor aggregate decrease with increasing χ, implying the considerable self-quenching of acceptor fluorescence. The relative change of the coherent size of the dye II aggregate has been estimated from the J-band line width and the radiative decay rate constant. It is found that the coherent size of the dye II aggregate is increased by a factor of 4−5 with increasing χ from 0.008 to 1.