Morphology and Reactivity of Polymers Prepared by Covalently Linking Cu(II) and Co(II) Sulfonated Phthalocyanines to a Polyacetamide Backbone. The Radical Reactions of Phthalocyanine Pendants in Bundles of the Polymer

G. FERRAUDI; G. RUIZ; G. LAPPIN; L. LEMUS

Turin – Italy

Congreso; 41st IUPAC World Chemistry Congress; 2007

The tetrasulfonated CuII(tspc)4-, tspc = 4,4´,4",4"´-phthalocyaninetetrasulfonate,  and the trisulfonated CoII(trspc)3-, trspc = n,n´,n"-phthalocyanine- trisulfonate and n, n’ and n” indicate the sulfonated positions of the various isomers, were covalently linked respectively to 1 in 5 and 1 in 10 amine groups of a polyethyleneimine, Mn ~ 10000 and Mw ~ 25000. Amine groups not converted to CuIIpc(-SO3)3(-SO2N<)– or CoIIpc(-SO3)2(-SO2N<)- pendants were acetlylated. Strands of the resulting polymers, poly(K3CuIItspc) and poly(K2CoIItrspc), formed spherical aggregates with diameters ~ 1000 nm for poly(K3CuIItspc) and ~ 100 nm for poly(K2CoIItrspc). ESR and UV-vis spectroscopies revealed that the phthalocyanine pendants were isolated and forming stacks in the strands of the polymer. Samples of the CuII(tspc) polymer aged periods of time longer than 24 h revealed a changing morphology of the polymers in solution. The detachment of the phthalocyanine complex from the backbone was detected in solutions aged several days.  Reactions of the pendants with pulse radiolytically generated radicals: e-sol, C•H2OH, (CH3)2COHC•H2, CO2•-, N3• and SO4•- revealed the distribution of pendants between isolated and aggregated forms. The reduction of the Cu(II) to Cu(II) was associated with pendants present in a mostly hydrophobic environment. Unstable phthalocyanine pendants with CoIII-Carbon bonds were observed when CoIIpc(-SO3)2(-SO2N<)- reacted with C-centered radicals, (CH3)2COHC•H2 and C•H2OH. The species with CoIII-Carbon bonds were precursors in the formation of CoIpc(-SO3)2(-SO2N<)-  pendants.