Interactions between a tetraanionic porphyrin and the methylviologen dication in methanol studied by fluorescence quenching reaction

Fluorescence decay curves for 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphine tetraanion (TPPS^4?) have been measured in the absence and presence of the methylviologen dication (MV²⁺) with various ionic strengths in methanol. In the presence of MV²⁺ the fluorescence decays can be expressed by a double exponential function, I(t = I₁exp(?t/τ₁) + I₂exp(?t/τ₂). The contribution by the faster decay component to the total fluorescence signal increases with increasing MV²⁺ concentration. The faster decay process is attributed to fluorescence from the excited state of a solvent-separated ion pair (SSIP) formed between TPPS^4? and MV²⁺, and the slower process is attributed to fluorescence from free TPPS^4? ions in the solution. Rate constants for the quenching of fluorescence from free TPPS^4? by MV²⁺ (k_q) and formation constants for the SSIP (K_SSIP) were calculated and both are found to decrease with increasing ionic strength. The decrease in k_q and K_SSIP values can be interpreted in terms of the shielding of electrostatic attraction between the ions.