The Effect of Macromolecular Architecture in Nanomaterials:  A Comparison of Site Isolation in Porphyrin Core Dendrimers and Their Isomeric Linear Analogues

The influence of macromolecular architecture on the physical properties of polymeric materials has been studied by comparing poly(benzyl ether) dendrons with their exact linear analogues. The results clearly confirm the anticipation that dendrimers are unique when compared to other architectures. Ph...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2002-04, Vol.124 (15), p.3926-3938
Main Authors: Harth, Eva M, Hecht, Stefan, Helms, Brett, Malmstrom, Eva E, Fréchet, Jean M. J, Hawker, Craig J
Format: Article
Language:English
Subjects:
Applied sciences
binding
block-copolymers
Chemistry
convergent approach
dendritic macromolecules
Exact sciences and technology
hyperbranched polymers
Kemi
metalloporphyrins
micelles
molecules
NATURAL SCIENCES
NATURVETENSKAP
Organic polymers
Physicochemistry of polymers
Properties and characterization
proton-transfer polymerization
star polymers
Structure, morphology and analysis
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Summary:The influence of macromolecular architecture on the physical properties of polymeric materials has been studied by comparing poly(benzyl ether) dendrons with their exact linear analogues. The results clearly confirm the anticipation that dendrimers are unique when compared to other architectures. Physical properties, from hydrodynamic volume to crystallinity, were shown to be different, and in a comparative study of core encapsulation in macromolecules of different architecture, energy transduction from the polymer backbone to a porphyrin core was shown to be different for dendrimers as compared to that of isomeric four- or eight-arm star polymers. Fluorescence excitation revealed strong, morphology dependent intramolecular energy transfer in the three macromolecular isomers investigated. Even at high generations, the dendrimers exhibited the most efficient energy transfer, thereby indicating that the dendritic architecture affords superior site isolation to the central porphyrin it surrounds.
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja025536u