Bimolecular electron transfer reactions in coumarin–amine systems: Donor–acceptor orientational effect on diffusion-controlled reaction rates

Abstract

Electron transfer (ET) reactions between excited coumarin dyes and different aliphatic amine (AlA) and aromatic amine (ArA) donors have been investigated in acetonitrile solution using steady-state (SS) and time-resolved (TR) fluorescence quenching measurements. No ground state complex or emissive exciplex formation has been indicated in these systems. SS and TR measurements give similar quenching constants ( k q) for each of the coumarin–amine pairs, suggesting dynamic nature of interaction in these systems. On correlating k q values with the free energy changes (Δ G 0) of the ET reactions show the typical Rehm–Weller type of behavior as expected for bimolecular ET reactions under diffusive condition, where k q increases with −Δ G 0 at the lower exergonicity (−Δ G 0) region but ultimately saturate to a diffusion-limited value ( k q DC ) at the higher exergonicity region. It is, however, interestingly observed that the k q DC values vary largely depending on the type of the amines used. Thus, k q DC is much higher with ArAs than AlAs. Similarly, the k q DC for cyclic monoamine 1-azabicyclo-[2,2,2]-octane (ABCO) is distinctly lower and that for cyclic diamine 1,4-diazabicyclo-[2,2,2]-octane (DABCO) is distinctly higher than the k q DC value obtained for other noncyclic AlAs. These differences in the k q DC values have been rationalized on the basis of the differences in the orientational restrictions involved in the ET reactions with different types of amines. As understood, n-type donors (AlAs) introduce large orientational restriction and thus significantly reduces the ET efficiency in comparison to the π-type donors (ArAs). Structural constrains are inferred to be the reason for the differences in the k q DC values involving ABCO, DABCO donors in comparison to other noncyclic AlAs. Supportive evidence for the orientational restrictions involving different types of amines donors has also been obtained from DFT based quantum chemical calculations on the molecular orbitals of representative acceptor and donor molecules.