Exciton energy transfer between optically forbidden states of molecular aggregates

Takayoshi Kobayashi, Takashi Taneichi, Shigehiro Takasaka
Journal of Chemical Physics 2007 May 21, 126 (19): 194705
3-ethyl-2-[3-(3-ethyl-2(3H)-benzoxazolylidene)-1-propenyl]benzoxazolium iodide (dye I) and pseudoisocyanine bromide are employed to form H aggregates as donors and J aggregates as acceptors. The energy of an H band of the H aggregates is higher than that of a J band of the J aggregates. It was confirmed that excitation of the H band does not emit fluorescence by comparison of excitation spectra of dye I H aggregates with that of dye I monomer. Absorption, fluorescence, and excitation spectra of spin-coated films of H aggregates mixed with various quantities of J aggregates have been observed. Excitation spectra probed at the J band are found to have a component of the H band. Fluorescence spectra originated from excitation of the H band are extracted and qualitatively analyzed. It is confirmed that excitation of the H band causes to emit fluorescence of a J band of the J aggregates. These phenomena show that exciton energy can transfer from the lowest energy in electronic states of the H aggregate, which state is optically forbidden, to electronic state of the J aggregate.

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