Inorganic Chemistry, Vol.38, No.11, 2705-2708, 1999
Multiphoton, multielectron transfer photochemistry in a soluble polymer
The effects of laser irradiance and quencher concentration on photochemical electron transfer in a Ru-II-bpy derivatized, polystyrene polymer have been studied. The polymer was a 1:1 copolymer of styrene:p-chloromethylstyrene with, on the average, similar to 30 repeat units in which each of the chloro groups was replaced by a [Ru-II(bpy)(2)(4-CH2O-4'-CH(3)bpy)](2+) chromophore by nucleophilic substitution. The abbreviation for the resulting polymer salt is [co-PS-CH2OCH2-(Ru-30(II))](PF6)(60). Upon visible excitation by laser flash photolysis at high irradiances, multiphoton excitation in the presence of high concentrations of the reductive quencher phenothiazine leads to individual polymeric strands that are reduced, on the average, by up to seven electrons to give PS-CH2OCH2- (Ru2+ Ru-23(7)+)](53+).
Keywords:ELECTRON-TRANSFER REACTIONS;TRANSITION-METAL COMPLEXES;N-ETHYLATED COPOLYMERS;CAGE ESCAPE YIELDS;ENERGY-TRANSFER;EXCITED-STATE;ELECTROCHEMICAL PROPERTIES;PHOTOINDUCEDELECTRON;REDOX SITES;METHYLVIOLOGEN