Control of photo-electron-transfer induced radical production by micellar cages, heavy-atom substituents and magnetic fields

Intramiceller radical pair formation and recombination kinetics in the electron transfer quenching of the thiomine triplet by aniline and various monohalogenated anilines have been studied by micro-second and nanosecond laser flash spectroscopy in reversed micellar solution of CDBA in benzene. Clear kinetic evidence of the micellar cage effect is provided by a comparative spectro-kinetical study in homogeneous aqueous and reversed micellar solution. In zero magnetic field the radical pairs which originate wrth a triplet spin alignment recombine in the waterpools of the micelles with a rate constant of about 3 × 106s-1 which is not sensitive to the hyperftue or spin-orbit coupling parameters of the aniline-type radical. Long lived radicals are formed by radical escape from the micelles occurring with a rate constant in the-order of 2 × 106s-1 and being insensitive to an external magnetic field. Intramicellar radical pair recombination is slowed down by an external magnetic field. A maximum effect (measured at 1 T) of a factor of 3 is observed for non-halogenated anilines. Halogen substituation attenuates this magnetic-field effect depending on the strength of spin-orbit coupling exhibited by the halogen substituent. The magnetic-field effect is interpreted in terms of the radical pair mechanism with special emphasis on the role of spin relaxation. Suppression of the magnetic-field effect by halogen substituents is attributed to the spin-rotational relaxation mechanism which is independent of a magnetic field. A heavy-atom suhstituent effect is also borne out in the primary yield of radical pairs which is decreased in the same way as in homogeneous solution. This is atttributed to the role of a triplet exciplex formed as a precursor of the radical pair, where heavy atom substitueuts cause very efficient rediationless decay to the ground state. A magnetic-field effect typical for the triplet mechanism in the exciplex has been detectable with 4-iodoaniline as quencher