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.

Heterometallic cooperativity in divalent metal ProPhenol catalysts: combining zinc with magnesium or calcium for cyclic ester ring-opening polymerisation

The first heterobimetallic lactide ROP catalysts based on two divalent metals outperform the homobimetallic analogues, attributed to the increased Lewis acidity of Mg or Ca (monomer coordination) and enhanced polarity of Zn–Et/OR (propagation).

Organocatalytic sequential ring-opening polymerization of cyclic ester/epoxide and N-sulfonyl aziridine: metal-free and easy access to block copolymers

Sequential ring-opening polymerization of ε-caprolactone (ε-CL)/propylene oxide (PO) and N-sulfonyl aziridine switched by tosyl isocyanate (TSI) allows the metal-free synthesis of polysulfonamide-based copolymers.

Organocatalytic sequential ring-opening polymerization of a cyclic ester and anionic polymerization of a vinyl monomer

The organocatalytic sequential block polymerization between a cyclic ester and a vinyl monomer is reported for the first time. The new block copolymer self-assembles into nanostructures leading to a thermoplastic elastomer-like material.

Supramolecular assembly by time-programmed acid autocatalysis

Coupling an acid-autocatalyzed clock reaction with the hydrolysis of a cyclic ester enables the time-domain programming of supramolecular pH-driven self-assembly.

Combining alkali metals and zinc to harness heterometallic cooperativity in cyclic ester ring-opening polymerisation

Cooperative heterotrimetallic Na/Zn2 and K/Zn2 complexes combine the excellent activities and control of the homometallic analogues, giving “best of both” in cyclic ester ring-opening polymerisation.

Vinylpyrroles: solid-state structures and aggregation-induced emission properties

A cyclic ester and a cyclic amide functionalized monopyrroles show aggregation-induced emission (AIE) by the restriction of intramolecular rotation (RIR) mechanism.