Spectroscopic and photophysical properties of ZnTPP in a room temperature ionic liquid

The steady-state absorption and emission spectra and the time-resolved Soret- and Q-band excited fluorescence profiles of the model metalloporphyrin, ZnTPP, have been measured in a highly purified sample of the common room temperature ionic liquid, [bmim][PF₆]. S₂-S₀ emission resulting from Soret-band excitation behaves in a manner completely consistent with that of molecular solvents of the same polarizability. The ionic nature of the solvent and its slow solvation relaxation times have no significant effect on the nature of the radiationless decay of the S₂ state, which decays quantitatively to S₁ at a population decay rate that is consistent with the weak coupling case of radiationless transition theory (energy gap law). The ratio of the intensities of the Qα:Qβ (0-0:1-0) bands is consistent with the solvatochromic shift correlation data obtained for molecular solvents. The temporal S₁ fluorescence decay profiles measured at a single emission wavelength are biexponential; the longer-lived major component is similar to that observed for ZnTPP in molecular solvents, and the minor shorter-lived component is attributed to solvent relaxation processes on a nanosecond time scale.