PHOTOINDUCED ELECTRON-TRANSFER TO METHYLVIOLOGEN FROM ZINC(II) TETRAPHENYLPORPHYRIN COMPARTMENTALIZED IN UNIMER MICELLES OF AMPHIPHILIC POLYELECTROLYTES

Zinc(II) tetraphenylporphyrin (ZnTPP) moieties are covalently attached to amphiphilic sodium polysulfonates carrying about 60 mol % of laury l (LA), 2-(naphthyl)methyl (Naph), or cyclododecyl (CD) groups. The Zn TPP moieties are compartmentalized within the hydrophobic clusters in aqueous solution, The charge transfer complexation of the compartmenta lized ZnTPP moieties with methylviologen (MV2+) is completely suppress ed, The electron transfer (ET) from the singlet excited state of the Z nTPP chromophore to MV2+ in the compartmentalized system is 2 orders o f magnitude Blower than that in a reference copolymer system having no hydrophobic groups. The apparent second-order rate constants for the ET from the triplet, excited state of the ZnTPP chromophore to MV2+ ar e almost equal in all the polymer systems. The accumulation of ZnTPP+. was observed as a result of the compartmentalization. The Naph and CD groups are more effective in the accumulation of ZnTPP+. than is the LA group. ZnTPP+. persisted over st period of milliseconds in the terp olymer systems containing the Naph and CD groups.