Formation and reactions of poly(4-vinylbiphenyl) anions in pulse radiolysis and γ-radiolysis: Comparison of their kinetic behavior with that of biphenyl anions

Abstract Formation, reactions and decay of poly(4-vinylbiphenyl) anions, formed by the radiolysis of 2-methyltetrahydrofuran (MTHF) solutions containing poly(4-vinylbiphenyl), were compared with those of biphenyl anions in the same solvent at 77–150 K. When a second solute, pyrene, was added to MTHF-poly(4-vinylbiphenyl) solutions, the electron transfer from poly(4-vinylbiphenyl) anions to pyrene molecules was directly observed by pulse radiolysis. The rate for the electron transfer reaction and the charge neutralization reaction, estimated from the decay curve of poly(4-vinylbiphenyl) anion, was of the same order of magnitude as that of biphenyl anions in MTHF solutions. A remarkable difference between poly(4-vinylbiphenyl) and biphenyl was observed for the electron capture reaction in MTHF at 77 K. The low efficiency of electron capture by poly(4-vinylbiphenyl) is ascribed to overlapping of the capture volume on the polymer chain.