Time-dependent density functional theory calculations of the solvatochromism of some azo sulfonamide fluorochromes

The absorption and emission spectra of three azo sulfonamide compounds in different solvents were investigated theoretically by using response functions combined with density functional theory (DFT), while the solvent effect on the structure and the electronic transitions was determined using the integral equation formalism for the polarizable continuum model (IEF-PCM). The results show that the applied different exchange-correlation functionals can reproduce the experimental values well. DFT calculations of the title compounds showed that the H-bond formed between the solute and solvent molecules is one of the major causes of the reversible solvatochromism observed in measured spectra. This is due to a better stabilization of the neutral form than the zwitterionic form in the polar protic solvents, which is characteristic of the hypsochromic shift. On the other hand, the molecules considered exhibit a monotonic behavior regarding the polarity of the low-lying excited state (Δμ(g–CT)) as a function of the solvent polarity. This dependence occurs in the case of the positive solvatochromism and confirms the thesis regarding the H-bond solute–solvent interactions. Theoretically determined values of the two-photon cross section revealed that the (σ(OF)((2))) shows similar trends with changes in λ(abs), in contrast to 〈δ(OF)〉 values. In conclusion, the results demonstrate that the investigated molecules can be used successfully as fluorochromes in bioimaging. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1007/s00894-015-2651-z) contains supplementary material, which is available to authorized users.