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The photochemical properties of a series of xanthene dye bis(diphenyliodonium) salts (XT(JPh2)2) were compared. The results of fluorescence quenching demonstrate that the electron transfer of XT(Iph2)2 is mainly from ion pair and the quenching rate constants approach 1011-12M-1s-1 that is well above the rate limit controlled by diffusion. Effects of halogen substituents in the ortho positions adjacent to phenoxyl group in xanthene moiety directly affect their photoreactivities and dark storage stabilities. XT(Iph2)2 salts were applicable for vinyl monomers and the efficiency of polymerization depends on the rate of photogeneration of active radicals. Effects of solvent polarity and concentration of XT(Iph2)2 were also investigated.

Photoinduced Polymerization via an Intra-Ion-Pair Electron Transfer Process.