Solvent effects on the S0(1(1)Ag-) --> S2(1(1)Bu+) transition of beta-carotene, echinenone, canthaxanthin, and astaxanthin in supercritical CO2 and CF3H.

Solvent-induced spectral shifts of the four C40 carotenoids, beta-carotene, echinenone, canthaxantin, and astaxanthin, have been studied in supercritical CO2 and CF3H. In situ absorption spectroscopic analysis was used to determine the maximum peak position of the electronic transitions from the ground state (1(1)Ag-) to the S2 state (1(1)Bu+) of the carotenoids. The medium polarizability function, R(n) = (n2 - 1)/(n2 + 2) of the refractive index of the solvent was varied over the range R(n) = 0.08-0.14, by changing the pressure of CO2 or CF3H between 90 and 300 bar at the temperature 308 K. For all the carotenoids studied here, a significant hypsochromic shift of ca. 20-30 nm was observed in supercritical fluids as compared to that in nonpolar liquids. The spectral shifts in supercritical fluids were compared with those in liquids and showed a clear linear dependence on the medium polarizability. The temperature-dependent shift of the absorption maxima was less significant. Interestingly, there was almost no difference in the energetic position of the absorption maxima in supercritical CO2 and CF3H at a given R(n) value. This is in contrast to previous extrapolations from studies in liquids at larger R(n) values, which yielded different slopes of the R(n)-dependent spectral shifts for polar and nonpolar solvents toward the gas-phase limit of R(n) = 0. The current experimental results in the gas-to-liquid range show that the polarity of the solvent has only a minor influence on the 1(1)Ag- --> 1(1)Bu+ transition energy in the region of low R(n). We also obtain more reliable extrapolations of this 0-0 transition energy to the gas-phase limit nu(0-0)(gas-phase) approximately (23,000 +/- 120) cm(-1) for beta-carotene.