INIFTA   05425
INSTITUTO DE INVESTIGACIONES FISICO-QUIMICAS TEORICAS Y APLICADAS
Unidad Ejecutora - UE
artículos
Título:
Preparation and redox reactions of pendent CO2RhIII(phthalocyanine) bound to a poly(acrylate) backbone. Effects of the backbone’s hypercoiling on the association of the macrocycle pendants and their photochemical and thermal redox reactions
Autor/es:
S. THOMAS; G. RUIZ; G. FERRAUDI
Revista:
MACROMOLECULES
Referencias:
Año: 2006 vol. 39 p. 6615 - 6621
ISSN:
0024-9297
Resumen:
Abstract A polymer of poly- (acrylic acid) derivatized with RhIII(pc) (pc = phthalocyanine) it was synthesized and characterized. The morphology of the chains of poly-RhIII(pc) was investigated by AFM microscopy having been observed a string of spherules indicated the hypercoiling of the poly-(acrylate) backbone. . Phthalocyanine pendants in a polymer with a 1:8 stoichiometric relationship of ---RhIII(pc) to ---CH2CH(CO2-)---- exhibited chemical properties different of the RhIII(tspc)-3 in aqueous medium or the XRhIII(pc), X = Cl, Br, I, in nonaqueous media. The reactivity of poly-RhIII(pc) was studied with reducing radicals like a e-sol, (CH3)2C●OH, NiL+ (L = [14]aneN4, Me6[14]aneN4), or oxidants, i.e., N3●, Cl2●-, Br2●- or NiL3+. The spectroscopy and the kinetics of the products formation were investigated with the technique of pulse radiolysis. The photophysical and photochemical processes of poly-RhIII(pc) were studied by laser flash photolysis. The lifetime of the excited state, t = 133 ns, correlates well with the slow component of the decay of the luminescence detected in the NIR region. This transient photogenerated has been assigned to a ligand field, LF, excited state not observed previously when XRhIII(pc) complexes were irradiated in homogenous solution. In this work, the thermal and photochemical properties of poly-RhIII(pc) are discussed based on the environmental conditions created by the chain of polymer