Several photoredox pairs containing dichromophoric hemicyanine dyes have been evaluated as novel photoinitiators for free radical polymerization induced with an argon-ion laser irradiation. The tested photoredox couples are the pairs composed of the hemicyanine dye cations acting as electron acceptors and n-butyltriphenyl borate anions being the electron donors. The photoinitiating abilities of the series of dimmeric dichromophoric stilbazolium borates; 1,2-: 1,3-; and 1,4-bis-[4-(p-N,N-dialkylaminostyryl)pyridinyl]xylene di-n-butyltriphenylborates, were compared to the photochemistry of structurally related, monochromophoric styrylpyridinium borates. The obtained results clearly documented that the dicationic photoinitiators exhibit a marked increase in the photoinitiation ability compared to the initiators consisting of a single charged hemicyanine dye. Our studies revealed also that the rate of photopolymerization depends on Delta G(el) of electron transfer between borate anion and styrylpyridinium cation. The latter value was estimated for all series of styrylpyridinium borate salts. The relationship between the rate of polymerization and the free energy of activation shows the dependence predicted by the classical theory of electron transfer. (C) 2008 Elsevier B.V. All rights reserved.