Abstract
The photophysics of dipyridyl ketones (DPKs) has been investigated in aqueous solutions as a function of pH using pulsed and steady-state emission spectroscopy and nanosecond laser flash photolysis. All six DPK isomers were found to emit phosphorescence in aqueous frozen solutions at 77 K, but only three of them exhibited phosphorescence emissions and showed triplet transient absorption at room temperature. From both phosphorescence and triplet–triplet absorption titrations, they revealed proton-transfer reactions in the excited state occurring at different pH/H0 values than the ground-state acid–base equilibrations. Comparing results from different techniques gave evidence that the carbonyl oxygen is involved in the triplet state protonation (pK*≈ 3.5–6) for the isomers where it conjugates with the ring nitrogen atom, while proton addition prevalently occurs on the nitrogen for the unconjugated meta–meta isomer. A second protolytic equilibrium (pK*≈–2 to –1.6) implies formation of nitrogen diprotonated ions for all the isomers. The presence of two positive charges in the molecules prevents further protonation at the carbonyl group in the ground states as well as in the excited states.
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