GENERATION OF IONIC SPECIES BY PHOTOLYSIS OF POLYSILYLENES IN DILUTE-SOLUTION

From flash photolysis studies (at lambda(inc) = 266 and 347 nm) involving the electrical conductivity and the optical absorption detection method it is inferred that poly(methylphenyl silylene), PMPSi, and poly(biphenylmethyl silylene), PBMSi, form ionic species in a monophotonic process in dilute tetrahydrofuran and dichloromethane solution at 295 K (phi(ion) approximate to 4 x 10(-2), PBMSI and 1 x 10(-2), PMPSi, in THF at lambda(inc) = 266 nm). The ionic species possess optical absorption bands between 350 and 500 nm with a maximum at about 380 nm. Both the photocurrent and the optical density at 380 nm decay with identical rates by a second order process (k(2) approximate to 3 x 10(11) dm(3) mol(-1) s(-1), PBMSi in THF at 295 K).