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Over the last decade, significant progress in supramolecular polymerization has had a substantial impact on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain-length, sequence, and stereochemical structure.

Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures, but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer.

Figure 1; Schematic illustration of conventional supramolecular polymerization
Supramolecular polymers are synthesized with molecules B through the connections between red and blue parts of B


Figure 2; Schematic illustration of precise supramolecular polymerization with an initiator
Molecule A (Initiator) connects with molecule B by opening up the intracyclic connection between the red and blue parts of B and forming a new connection.  The resulting dimer A-B possesses a free blue part and it connects the other B, which results in the formation of the trimer A-B-B.  This process will be repeated until all molecules B are consumed.

To learn more about this research, please view the full research report entitled "A Rational Strategy for the Realization of Chain-Growth Supramolecular Polymerization" at this page of the Science website.

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