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Thermodynamic changes in the photoinduced proton-transfer reaction of the triplet state of safranine-T.

The enthalpy and volume changes occurring in the triplet excited state proton-transfer reactions of safranine-T (SH+) in aqueous solutions at pH 4.8, 8.3, and 10.4 were investigated using time-resolved photoacoustics (TRP). The transient triplet state species were also studied using laser-flash photolysis (LFP). The LFP experiments showed the prompt formation of 3SH+ with a triplet quantum yield phiT = 0.28 between pH 4.8 and 10.4. At pH 8.3 3SH+ decays directly to the ground state. However, at pH 4.8 and 10.4, 3SH+ reacts with protons or hydroxy ions to form the dication 3SH2(2+) or the neutral 3S species, with diffusion-controlled rate constants of kH+ = 1.6 x 10(10) M(-1) s(-1), and kHO- = 2.6 x 10(10) M(-1) s(-1), respectively. Under the same experimental conditions, the TRP measurements allowed the accurate determination of the energy content of the rapidly formed triplet state 3SH+ i.e. E(T) = 175 kJ mol(-1). The slow component (0.1-3 micros) of the TRP signal at pH 4.8 and 10.4 was attributed to the formation of the species 3SH2(2+) and 3S, respectively. The enthalpy changes associated with the proton-transfer reactions of 3SH+, calculated from the values of the heat released as obtained by TRP, were in remarkable agreement with the values estimated from the thermodynamic data of the acid-base equilibria of the triplet states of the dye. The formation of 3SH+ was accompanied by a volume expansion of 1.8 cm3 mol(-1), which was explained by changes in the hydrogen-bonding interaction of the dye with its solvation sphere. Instead, the volume changes observed upon the formation of 3SH2(2-) and 3S accounted for the electrostrictive effect produced by the change in the charge distribution on the dye after the proton-transfer reaction.