Phase Selective Second Harmonic AC Voltammetry and Ultraviolet Photoelectron Spectroscopy for Evaluation of Electronic Structures of Cyanine Dyes

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Abstract
Reduction and oxidation potentials ( and , respectively) of cyanine dyes have been measured by phase selective second‐harmonic (PSSH) ac voltammetry and their ionization energy by photoelectron spectroscopy (UPS) to confirm the following relations [1] [2] where and are the heights of highest occupied molecular orbital and lowest unoccupied molecular orbital, respectively, and and are constants. The errors of and in dc polarography due to the following‐up chemical reactions of the dyes in acetonitrile could be reduced by PSSH voltammetry, and and were correlated well with the molecular structures of the dyes. The good linear relationship between and of cyanine dyes supported the appropriateness of using and as the measures of and of the dyes, respectively. Good correlations were observed between and the efficiency of the light‐induced electron transfer from cyanine dyes to silver bromide microcrystals and between and the concentration of positive holes trapped by cyanine dyes.

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