Effect of Ionic Liquids as Cosurfactants on Photoinduced Electron Transfer in Tetronic Micelles

This study investigates the role of varying alkyl chain lengths of a series of surface-active 1-alkyl-3-methylimidazolium tetrafluoroborate ([C _nMIm][BF₄], n = 4, 6, and 10) ionic liquids (ILs) as cosurfactants in modifying the micellar characteristics of a tetronic star-block copolymer, T1304, and the consequent effects on bimolecular photoinduced electron transfer (PET) reactions carried out in these T1304-IL mixed micellar systems. Using coumarin 153 as the probe dye and following ground-state absorption, steady-state fluorescence, and time-resolved emission measurements, the micropolarity, microviscosity, and solvent relaxation dynamics in the micellar palisade layer have been revealed both in pure T1304 and in T1304-IL systems. With increasing alkyl chain length of the ILs, the palisade layer of the micelles gradually becomes more polar and less viscous, suggesting better incorporation of the longer alkyl chain length ILs as cosurfactants into the T1304 micelles. The bimolecular PET reactions, involving 7-aminocoumarins as acceptors and N, N-dimethylaniline as the donor, are considerably modulated in T1304 micelles by the presence of the ILs, the effect being more prominent for ILs with longer alkyl chain lengths. In all of the micellar systems, correlations of the electron transfer (ET) kinetics with the reaction exergonicity (-Δ G⁰) show clear Marcus inversion (MI) behavior where onsets of MI invariably appear at significantly lower exergonicities, suggesting the involvement of a two-dimensional ET mechanism. Interestingly, the Marcus correlations display significant variations, namely, enhanced reaction rates and gradual shift in the onset of MI toward higher exergonicity, as longer alkyl chain length ILs are sequentially introduced as cosurfactants. From the observed results, it is convincingly realized that 1-alkyl-3-methylimidazolium-based ILs can be used satisfactorily as cosurfactants in tetronic star-block copolymer solutions to modulate PET reactions very significantly for their better utilizations in suitable applied areas.