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While scattering techniques provide information about the dimensions of the dendritic molecules and their density profiles they are not sensitive to branching defects.
However, these studies do not yield direct information on the occurrence and frequency of structural defects because of their focus on ideally branched structures.
The synthetic regimes outlined above reflect a distinctive form of steric hindrance.
The dendrons can be attached to point-like cores, to linear polymer chains or to surfaces thus giving rise to three leading structural families of dendritic molecules: dendrimers.
Classical theory predicts that branching defects are unavoidable in large dendritic molecules when steric congestion is important.
Here we report first experimental evidence of this effect via labelling measurements of an extended homologous series of generations g=1…6 of dendronized polymers.
This technique is especially useful at high g and high molecular masses (MM) where the traditional analytical methods are challenged.
It is particularly suitable for the study of g effects diagnosed via defect quantification at high g.
This system exhibits a single type of defect interrogated specifically by the Sanger reagent thus permitting to identify the predicted upturn in the number of branching defects when g approaches g and the polymer density approaches close packing.