Influence of heterogeneity of confined water on photophysical behavior of acridine with amines: a time-resolved fluorescence and laser flash photolysis study.

The photophysical behavior of acridine (Acr) shows facilitated water-assisted protonation equilibrium between its deprotonted (Acr* ∼ 10 ns) and protonated forms (AcrH(+*) ∼ 28 ns) within confined region of ordered water molecules inside AOT/H(2)O/n-heptane reverse micelles (RMs). The time-resolved-area-normalized-emission spectra confirm both Acr* and AcrH(+*), while time-resolved-emission spectra depict time evolution between them. Quenching of AcrH(+*) with N,N-dimethylaniline (DMA) is a purely diffusion-controlled bimolecular quenching with linear Stern-Volmer (S-V) plot, while nonlinearity arises with triethylamine (TEA) that forms ground state complex with AcrH(+) (AcrH(+)··H(2)O··TEA) indicating both static and dynamic quenching. Transient intermediates, DMA(•+) and AcrH(•) infer photoinduced electron transfer from DMA to Acr, while those from AcrH(+)··H(2)O··TEA complex suggest water mediated excited-state proton transfer (ESPT) between AcrH(+) and TEA. The ESPT becomes faster in larger RMs due to enhanced mobility of hydronium ions in AcrH(+)··H(2)O··TEA, which reduces in smaller RMs as water becomes much more constrained owing to stronger complexation by excess confinement.