Sequence modification in copoly(ester-imide)s: a catalytic/supramolecular approach to the evolution and reading of copolymer sequence information

Catalytic ester-interchange reactions, analogous to mutation and recombination, allow new sequence information to be written statistically into poly(ester-imide) chains based on NDI (1,4,5,8-naphthalenetetracarboxylic diimide) units. Thus, both the insertion of the cyclic ester cyclopentadecanolide (“exaltolide”) into an NDI-based homopolymer and quantitative sequence exchange between two different homopoly(ester-imide)s are catalyzed by di- n -butyl tin(IV) oxide. Emerging sequences are identified at the triplet and quintet levels using supramolecular complexation of pyrene- d 10 at the NDI residues to amplify the separation of 1 H NMR resonances associated with different sequences. In such systems, pyrene is able to act as a “reader molecule” by generating different levels of ring-current shielding from the different patterns of supramolecular binding to all NDI-centered sequences of a given length. Catalytic ester-interchange reactions allow new sequence information to be written statistically into poly(ester-imide) chains based on NDI (1,4,5,8-naphthalenetetracarboxylic diimide) units. Insertion of the cyclic ester cyclopentadecanolide (“exaltolide”) into an NDI-based homopolymer and quantitative sequence exchange between two different homopoly(ester-imide)s are both catalyzed by di- n -butyl tin(IV) oxide. Emerging sequences from these reactions are identified using pyrene- d 10 as a “reader molecule” that binds rapidly and reversibly to the NDI residues, and amplifies the separation of 1 H NMR resonances associated with different sequences via cumulative aromatic ring-current shielding.