Photophysical properties of free base tetraphenylporphyrin and its zinc analog are investigated in detail in solvents of varying polarity by using steady state and time-resolved techniques. Both the porphyrins are excited at the Soret band to have better signal-to-noise ratio. Also, the fluorescence emission measurements are carried out by using dilute solutions (~10(-7)mol/L) of the fluorophores in order to minimize the self-quenching effect. It is observed that the steady state absorption and emission characteristics of the porphyrin molecules are mainly affected by polarizability (via refractive index) rather than polarity (via dielectric constant) of the moderate to highly polar solvents. As the molecules are highly symmetric in the ground state, the associated dipole moments are found to be very low from quantum chemical calculations performed by density functional theory method by using Gaussian 03 package. The dipole moments associated with the first excited singlet state of the porphyrins are computed by applying solvatochromic Stokes' shift method. To the best of our knowledge, this is the first attempt to calculate the excited state dipole moments of the porphyrins used in the present investigations. Also, fluorescence quantum yield, fluorescence lifetime of the first excited singlet state, radiative and non-radiative rate constants of the porphyrins are reported in solvents of varying polarity.
Keywords: Dipole moment; Lippert–Mataga equation; Porphyrin; Solvent polarity; Stokes’ shift.
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