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

Co-polycondensation of the diimide-based diols ,'-bis(2-hydroxyethyl)hexafluoroisopropylidene-diphthalimide, (HFDI), and ,'-bis(2-hydroxy-ethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide, (NDI), with aliphatic diacyl chlorides ClOC(CH) COCl ( = 5 to 8) affords linear copoly(ester-imide)s. Such copolymers interact with pyrene supramolecular binding of the polycyclic aromatic at NDI residues. This interaction results in upfield complexation shifts and sequence-related splittings of the NDI H NMR resonances, but gives a very different final resonance-pattern from the copolymer where = 2. Computational modelling of the polymer with = 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 = 2. The new single-site binding model enables the pattern of H NMR resonances for copolymers with longer spacers ( = 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.