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Spectroscopic properties of azobenzene-based pH indicator dyes: A quantum chemical and experimental study

: Escudero, D.; Trupp, S.; Bussemer, B.; Mohr, G.J.; Gonzalez, L.


Journal of chemical theory and computation : JCTC 7 (2011), Nr.4, S.1062-1072
ISSN: 1549-9618
ISSN: 1549-9626
Fraunhofer EMFT ()

The UV visible absorption spectra of six new optical sensors based on acidochromic azobenzenes have been measured and assigned with the help of quantum chemical calculations. The investigated compounds are able to monitor the pH in the range from pH 3-10. Using the hybrid density functional PBEO and including solvent effects with a polarized continuum model, the agreement between the experimental and theoretical UV/vis spectra of the dyes in their neutral and anionic forms is very good. The spectroscopic pi pi* states, responsible for the optical properties of the sensors, are described within an accuracy of 0.1 eV. Similar accuracy is demonstrated in the ne states. The pi pi* states can be assigned as a charge transfer from the aromatic pi orbital localized in the azo-phenol moiety to the antibonding pi* of the azo group. Under basic conditions, the spectrum is bathochromically shifted and more intense than in acid media. Upon substitution in the phenyl moiety, red- or blue-shifts of the UV visible bands are observed depending on whether the substituent is electron-donor or -withdrawing, respectively. These effects are stronger at high pH values and can be rationalized in terms of the stabilization and/or destabilization of the involved frontier orbitals.