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Co-polycondensation of the diimide-based diols N , N '-bis(2-hydroxyethyl)hexafluoroisopropylidene-diphthalimide, (HFDI), and N , N '-bis(2-hydroxy-ethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide, (NDI), with aliphatic diacyl chlorides ClOC(CH 2 )  x  COCl ( x = 5 to 8) affords linear copoly(ester-imide)s. Such copolymers interact with pyrene via supramolecular binding of the polycyclic aromatic at NDI residues. This interaction results in upfield complexation shifts and sequence-related splittings of the NDI 1 H NMR resonances, but gives a very different final resonance-pattern from the copolymer where x = 2. Computational modelling of the polymer with x = 5 suggests that each pyrene molecule binds to just a single NDI residue rather than by intercalation between a pair of NDI's at a tight chain-fold, as was found for x = 2. The new single-site binding model enables the pattern of 1 H NMR resonances for copolymers with longer spacers ( x = 5 to 8) to be reproduced and assigned by simulation from sequence-specific shielding factors based on a type of fractal known as the last-fraction Cantor set. As this type of fractal also enables an understanding of pairwise binding systems, it evidently provides a general numerical framework for supramolecular sequence-analysis in binary copolymers.

Single-site binding of pyrene to poly(ester-imide)s incorporating long spacer-units: prediction of NMR resonance-patterns from a fractal model