Origin of the coloration and structure of azobenzene chromogen

Autor: Yu. A. Ershov, L. N. Guseva, Yu. A. Mikheev
Rok vydání: 2015
Předmět:
Zdroj: Russian Journal of Physical Chemistry A. 89:2036-2050
ISSN: 1531-863X
0036-0244
Popis: Enhancement of the visible (VIS) absorption band intensity of trans-azobenzene (t-AB) in solutions containing water and hydrogen ions is established. This contradicts the current belief that it is part of the n → π* transition. At the same time, it qualitatively reflects the properties of the π → π* bands of protonated azobenzene (ABH+). It is concluded that t-AB molecules display an autopolarization property and exist in the form of two individual electronic (e) tautomers. One of these is nonpolar and has the canonical chemical structure; its content considerably exceeds that of the polar e-tautomer. The polar e-tautomer forms as a result of the reversible transfer of an electron from the nonbonding donor sp 2 orbital of nitrogen to the nonbonding acceptor Rydberg’s 3S orbital (R 3S ) of the local N=N chromophore within the molecule. The positively charged chromogen corresponding to it displays a π → π* transition in the visible spectral region, and the π→π* transition (not the traditionally postulated n → π* transition) is clearly responsible for the orange color of AB. A model of transient e-configurations with the participation of R 3S and explaining the previous poorly understood experimental results from optical absorption, fluorescent, raman spectroscopic, and photoionization femtosecond kinetic studies is considered. It is shown that famous ideas about the violation of Kasha’s rule in t-AB fluorescence and photoisomerization processes are incorrect. The reasons for the increased intensity of the VIS band of cis-azobenzene (c-AB) are explained. It is concluded that there is an equilibrium between nonpolar and polarized e-tautomers in cis-azobenzene as well, but it is shifted more toward the polar tautomer in c-AB due to its structural features, making the VIS band more intense.
Databáze: OpenAIRE
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