Picosecond Laser Photolysis Studies on Chain-Length, Solvent and Temperature Dependences of the Intramolecular Photoreduction Process of Benzophenone by Diphenylamine

Photoinduced hydrogen abstraction (HA) processes of 1-(4-anilinophenyl)-2-(4-benzophenoxy)ethane, 1-(4-anilinophenyl)-3-4-benzophenoxy)propane, and 1-(4-anilinophenyl)-8-(4-benzophenoxy)octane (BP–O–(CH2)n–O–DPA: n = 2, 3, and 8) in benzene, acetonitrile, and N,N-dimethylformamide solutions were investigated by means of picosecond transient absorption spectroscopy. In benzene solution, apparent mechanism of the hydrogen abstraction reaction was “direct” process and no absorption spectrum of the charge separated state was observed. The decay of triplet benzophenone moiety (3BP*) was regulated by the dynamic rearrangement process of the mutual geometry between 3BP* and DPA to a more compact one. In polar solutions, the electron transfer (ET) from DPA to 3BP* moiety took place in addition to the direct HA from DPA by 3BP*. The rate of the ET reaction was regulated mainly by the distance between the reactant moieties. Moreover, the intra-ion pair (IP) proton transfer (PT) resulting in the HA product formation was observed, although such PT process in the IP state between the unlinked 3BP* and the secondary amine was not observed. By integrating the present results on the linked systems with those of the unlinked systems, the role of the ET or CT interaction in the HA process of 3BP* from the secondary amine was discussed.