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Excited state vs. photoinduced charge separation in bundles of a polyamide containing pendant AlIII phthalocyaninetetrasulfonate groups. Potential applications to photocatalysis

Paper ID Volume ID Publish Year Pages File Format Full-Text
27745 44041 2009 9 PDF Available
Title
Excited state vs. photoinduced charge separation in bundles of a polyamide containing pendant AlIII phthalocyaninetetrasulfonate groups. Potential applications to photocatalysis
Abstract

A new polyimide containing pendant AlIIIphthalocyaninetetrasulfonate groups, [HOAlIII(pc)(SO3−)3(SO2N<)]\3, was synthesized and the morphology of the polymer, poly(HOAlIIItspc), in aqueous solutions was investigated using transmission electron microscopy and UV–vis absorption and emission spectroscopies. The strands of poly(HOAlIIItspc) are associated in near spherical bundles with ∼150 nm diameter in aqueous solutions. Most of the pendants in the bundles are forming π-stacks where the largest fraction of them must be dimers. Flash photochemical observations in a 0.15 ps to 100 μs time domain revealed the photogeneration of pendant radicals, pendant2− and pendant4−. This process stands in contrast with the photochemistry that tetrasulfonated AlIII phthalocyanine shows under the same experimental conditions of poly(HOAlIIItspc). The kinetics of the phthalocyanine radicals formation and disappearance is consistent with energy and charge transfers between phthalocyanine pendants in the bundle. Radical scavengers (methylviologen, O2, cathecol, lignine) present in the solutions of poly(HOAlIIItspc) trapped the phthalocyanine radicals demonstrating that scavenging reactions can compete with the slow radical–radical annihilation process and used for the photocatalysis of redox processes.

Keywords
Polymer; Pendant-Al(III)phthalocyanine; Energy and electron transfers; Pendant radicals; Photocatalysis
First Page Preview
Excited state vs. photoinduced charge separation in bundles of a polyamide containing pendant AlIII phthalocyaninetetrasulfonate groups. Potential applications to photocatalysis
Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 206, Issue 1, 5 July 2009, Pages 1–9
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering