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-d10 at the NDI residues to amplify the separation of 1H 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.

Sequence-Modification in Copoly(ester-Imide)s: A Catalytic/supramolecular Approach to Writing/reading Copolymer Sequence-Information

Catalytic ester-interchange reactions, analogous to mutation and recombination, allow new sequence-information to be written, statistically, into NDI-based poly(ester-imide) chains. Thus, insertion of the cyclic ester cyclopentadecanolide ("exaltolide") into an NDI-based homopolymer, and quantitative sequence-exchange between two different homopoly(ester-imide)s, are catalysed by di-<i>n</i>-butyl tin(IV) oxide. Emerging sequences are identified at the triplet and quintet levels by ¹H NMR analysis, using supramolecular complexation of pyrene-<i>d</i>₁₀ at the NDI residues to amplify the separation of 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 the NDI-centred sequences of a given length.

Sequence-Modification in Copoly(ester-Imide)s: A Catalytic/supramolecular Approach to Writing/reading Copolymer Sequence-Information

Catalytic ester-interchange reactions, analogous to mutation and recombination, allow new sequence-information to be written, statistically, into NDI-based poly(ester-imide) chains. Thus, insertion of the cyclic ester cyclopentadecanolide ("exaltolide") into an NDI-based homopolymer, and quantitative sequence-exchange between two different homopoly(ester-imide)s, are catalysed by di-<i>n</i>-butyl tin(IV) oxide. Emerging sequences are identified at the triplet and quintet levels by ¹H NMR analysis, using supramolecular complexation of pyrene-<i>d</i>₁₀ at the NDI residues to amplify the separation of 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 the NDI-centred sequences of a given length.