Probing of Higher Excited States of Merocyanine Derivatives of Azaazulene and Indandione by Fluorescence Excitation Anisotropy Spectra
This paper is dedicated to the spectral and quantum-chemical studies of higher excited states of merocyanine derivatives of azaazulene and indandione. A particular attention is paid to the analysis of fluorescence excitation anisotropy spectra of the mentioned compounds. The long-wave shift by ≈ 50 nm of a deep clear minimum in the fluorescence excitation anisotropy spectrum due to an elongation of the polymethine dye chromophore is established. Such shift is close in a value to the bathochromic shift of the first minimum in the anisotropy spectrum of symmetric ionic polymethine dyes, in which this minimum corresponds to the second electronic transition. The parallel spectral study and quantum-chemical calculations allowed us to correctly interpret the fluorescence excitation anisotropy spectra of merocyanines and relate the first clear minimum with the seventh electronic transition. The last resembles the second electronic transition between delocalized molecular orbitals (MO) in polymethine dyes.
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