Morphology and radical reactions of Cu(II) and Co(II) sulfonated phthalocyanines covalently linked to poly(ethyleneamide)

作者：Ruiz Gustavo T; Lappin Alexander G; Ferraudi Guillermo^*

来源：Journal of Porphyrins and Phthalocyanines, 2010, 14(1): 69-80.

DOI：10.1142/S1088424610001751

• phthalocyanine-derivatized poly(ethylenimine)
• copper
• sulfonated phthalocyanine
• cobalt
• phthalocyanine radicals
• pulse radiolysis
• reaction kinetics
• reaction intermediates

The tetrasulfonated Cu(II)(tspc)(4-), tspc = 4,4',4 '',4'"-phthalocyaninetetrasulfonate, and the trisulfonated Co(II)(trspc)(3-), trspc = n,n',n ''-phthalocyanine-trisulfonate and n, n' and n '' indicate the sulfonated positions of the various isomers, were covalently linked to a polyethyleneimine, M(n) similar to 10000 and M(w) similar to 25000, backbone. A fraction of the amine groups in a strand was converted to Cu(II)pc(-SO(3))(3) (-SO(2)N<)(\3-) or Co(II)pc(-SO(3))(2)(-SO(2)N<)(\2-) pendants and the remaining were acetylated. Strands of the polymers, poly(K(3)Cu(II)tspc) and poly(K(2)Co(II)trspc), formed spherical bundles with diameters similar to 1000 nm for poly(K(3)Cu(II)tspc) and similar to 100 nm for poly(K(2)Co(II)trspc). The stability of the bundles is metal-dependent. Poly(K(2)Co(II)trspc) forms the most stable bundles with respect to hydrolytic and redox reactions. ESR and optical spectroscopies as well as reactions of the pendants with pulse radiolytically generated radicals, namely e(sol)(-), C(center dot)H(2)OH, (CH(3))(2)COHC(center dot)H(2), CO(2)(center dot-), N(3)(center dot) and SO(4)(center dot-), revealed a distribution of pendants between isolated and aggregated forms in a bundle. The reduction of the Cu(II) to Cu(I) in aqueous solutions of the poly(K(3)Cu(II)tspc) was associated with pendants present in a mostly hydrophobic environment. Unstable phthalocyanine pendants with Co(III)-carbon bonds are formed when Co(II)pc(-SO(3))(2)(-SO(2)N<)(\2-) reacted with C-centered radicals, (CH(3))(2)COHC center dot H(2) and C(center dot)H(2)OH. The species with Co(III)-carbon bonds were precursors to the formation of Co(I)pc(-SO(3))(2)(-SO(2)N<)(\3-) pendants. The redox reactions of the pendants in these polymers are compared with those of K(4)Cu(II)tspc and K(3)Co(II)trspc.

• 出版日期2010-1