Excited‐State Behavior and Photoionization of 1,8‐Acridinedione Dyes in Micelles—Comparison with NADH Oxidation

Abstract

The photophysics and photochemistry of 1,8-acridinedione dyes, which are analogues of reduced nicotinamide adenine dinucleotide (NADH), are studied in anionic and cationic micelles. Acridinedione dyes (ADDs) are solubilized in micelles at the micelle-water interface and are in equilibrium between the aqueous and micellar phase. The binding of the ADDs with micelles is attributed to hydrophobic interactions and the binding constants are determined with steady-state and time-resolved techniques. Nanosecond laser flash photolysis studies are carried out in aqueous, anionic, and cationic micellar solutions. The ADD undergoes photoionization in the excited state to give a solvated electron. The solvated electron reacts with the ADD to give an anion radical. In anionic micelles, the yield of the solvated electron increases because of the efficient separation of the cation radical and the electron. Cation radicals derived from the photooxidation of ADDs are involved in keto-enol tautomerization. Under acidic conditions, an enol radical cation of the acridinedione dye is formed from the keto form of the cation radical by intramolecular hydrogen atom transfer. In cationic micelles, due to electrostatic attraction, the electron cannot escape from the micelle and recombination of the cation radical and the electron results in the formation of a triplet state. For the first time, a solvated electron is observed in the laser flash photolysis of ADDs in anionic micelles. The photoionization of ADDs depends on the excitation wavelength and is biphotonic at 355 nm and monophotonic at 248 nm. From the results with this NADH model compound, the sequential electron-proton-electron transfer oxidation of NADH is confirmed and the nature of the intermediates involved in the oxidation is unraveled; these intermediates are found to depend on the pH value of the medium.