On Saltiel's isopolarizability approach and its applicability to diphenylpolyenes

•The thermochromism of polyenes is not merely the echo of the polarizability of the medium.•The structural influence on the thermochromic behavior of polyenes.•Increasing viscosity of the medium decreases the structural contribution to the thermochromism of polyenes. Based on solvatochromic and ther...

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Bibliographic Details
Published in:Chemical physics letters 2015-08, Vol.635, p.56-59
Main Author: Catalán, Javier
Format: Article
Language:English
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Summary:•The thermochromism of polyenes is not merely the echo of the polarizability of the medium.•The structural influence on the thermochromic behavior of polyenes.•Increasing viscosity of the medium decreases the structural contribution to the thermochromism of polyenes. Based on solvatochromic and thermochromic data for diphenylpolyenes of the general formula H5C6(CHCH)nC6H5, with n=1–4, it has been found that their thermochromism is influenced not only by the polarizability of the medium but also by a conformational effect that is at least as strong as that of their solvatochromism. As shown here, the conformational effect enhances the bathochromic band shift caused by lowering the temperature of the solvent. However, such an effect does not occur in structurally rigid diphenylpolyenes. Consequently, Saltiel's isopolarizability approach does not hold in polyenes.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2015.06.043