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1.
ACS Cent Sci ; 9(8): 1703-1704, 2023 Aug 23.
Article in English | MEDLINE | ID: mdl-37637750

ABSTRACT

[This corrects the article DOI: 10.1021/acscentsci.3c00032.].

2.
ACS Cent Sci ; 9(6): 1104-1110, 2023 Jun 28.
Article in English | MEDLINE | ID: mdl-37396860

ABSTRACT

Controlled incorporation of nitrogen into macromolecular skeletons is a long-standing challenge whose resolution would enable the preparation of soft materials with the scalability of man-made plastics and functionality of Nature's proteins. Nylons and polyurethanes notwithstanding, nitrogen-rich polymer backbones remain scarce, and their synthesis typically lacks precision. Here we report a strategy that begins to address this limitation founded on a mechanistic discovery: ring-opening metathesis polymerization (ROMP) of carbodiimides followed by carbodiimide derivatization. An iridium guanidinate complex was found to initiate and catalyze ROMP of N-aryl and N-alkyl cyclic carbodiimides. Nucleophilic addition to the resulting polycarbodiimides enabled the preparation of polyureas, polythioureas, and polyguanidinates with varied architectures. This work advances the foundations of metathesis chemistry and opens the door to systematic investigations of structure-folding-property relationships in nitrogen-rich macromolecules.

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