Fate of Photoinduced Electron Transfer Reactions with Temperature- and pH-Induced Assembly/Disassembly of Star Block...

The assembly/disassembly of star block copolymers induced by changes in temperature or pH of the medium is anticipated to have interesting implications for hosting/releasing drugs and tuning chemical reactions. This study investigates the possibility of employing the dually sensitive self-assembly of an ethylene oxide-propylene oxide star block copolymer, Tetronic T904, to influence photoinduced electron transfer (ET) reactions, on switching from the assembled state (micelle) when temperature is above the critical micelle temperature (CMT) and pH of the medium is above the pK_a of T904 to the dissociated (unimer) state when either the temperature is below the CMT or the polymer is protonated. Steady-state and time-resolved fluorescence techniques have been used to characterize the microenvironments of the reactants in T904 solutions under different temperature and pH conditions and to determine ET rate constants. Interestingly, the bimolecular ET rate constants in both assembled and disassembled states of T904 depict a bell-shaped correlation with the driving force of the reaction, in accordance with Marcus inversion behavior instead of the usual Rehm-Weller behavior seen in conventional solvents. The assembly/disassembly of T904 stimulated by temperature or pH affects the micropolarity in the reactant environment, the magnitude of ET rate constants, and the position of inversion on the exergonicity scale.