Solvent Dependent Dynamics of Salicylidene Aniline in Binary Mixtures of Supercritical CO2 with 1‑Propanol or Cyclohexane

• Published in: The journal of physical chemistry. B Vol. 121; no. 4; pp. 835 - 842
• Main Authors: Kieda, Ryan D, Dunkelberger, Adam D, Case, Amanda S, Crim, F. Fleming
• Format: Journal Article
• Language: English
• Published: American Chemical Society 02.02.2017
• Subjects: 1-propanol; absorption; aniline; carbon dioxide; cyclohexanes; solutes; solvents; spectroscopy; temperature; viscosity
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/acs.jpcb.6b05959

The role of different solvent environments in determining the behavior of molecules in solution is a fundamental aspect of chemical reactivity. We present an approach for exploring the influence of solvent properties on condensed-phase dynamics using ultrafast transient absorption spectroscopy in supercritical CO2. Using supercritical CO2 permits adjustment of the density, by varying the temperature and pressure, whereas varying the concentration or identity of a second solvent, the cosolvent, in a binary mixture allows for adjustments of the degree of interaction between the solute and the solvent. Salicylidene aniline, a prototypical excited-state intramolecular proton-transfer system, is the subject of this study. In this system, the decay rate of the transient absorption signal decreases as the fraction of the cosolvent (for both 1-propanol and cyclohexane) increases. The decay rate also decreases with an increase in the viscosity of the mixture, but the effect is much larger for the 1-propanol cosolvent than for cyclohexane. These observations illustrate that the decay rate of the photoexcited salicylidene aniline depends on more than just the solvent viscosity, suggesting that properties such as polarity also play a role in the dynamics.