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The Absorption Spectrum of cis-Azobenzene

Abstract

Azobenzene is a prototypical photochromic molecule existing in two isomeric forms, which has numerous photochemical applications that rely on a precise knowledge of the molar absorption coefficients (ε). Careful analysis revealed that the previously reported absorption spectra of the ”pure” isomers were in fact mutually contaminated by small amounts of the other isomer. Therefore, the absorption spectra of both trans- and cis-azobenzene in methanol were re-determined at temperatures of 5-45 °C. The thermodynamically more stable trans-azobenzene was prepared by warming the solution in the dark. To obtain the spectrum of the cis-azobenzene three methods were used, which gave consistent results within the limits of error. The method based on the subtraction of derivative spectra coupled with a global analysis of spectra recorded during thermal cis-trans isomerization is shown to give slightly more reliable results than the method using isomeric ratios determined by 1H-NMR. The described methods are readily generalizable to other azobenzene derivatives and to other photochromic systems. The practical implication of the re-determined ε values is demonstrated by a very high precision of spectrophotometric species analysis in azobenzene isomeric mixtures. The new ε values imply that the previously reported quantum yields must be revised.

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Publication details

The article was received on 18 Aug 2017, accepted on 06 Nov 2017 and first published on 09 Nov 2017


Article type: Paper
DOI: 10.1039/C7PP00314E
Citation: Photochem. Photobiol. Sci., 2017, Accepted Manuscript
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    The Absorption Spectrum of cis-Azobenzene

    Ľ. Vetráková, V. Ladányi, J. Al Anshori, P. Dvořák, J. Wirz and D. Heger, Photochem. Photobiol. Sci., 2017, Accepted Manuscript , DOI: 10.1039/C7PP00314E

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