Simultaneous and in situ syntheses of an enantiomeric pair of homochiral polymers as their perfect stereocomplex in a crystal

Autor: Ravichandran Khazeber, Sourav Pathak, Kana M. Sureshan
Jazyk: angličtina
Rok vydání: 2024
Předmět:
Zdroj: Nature Communications, Vol 15, Iss 1, Pp 1-8 (2024)
Druh dokumentu: article
ISSN: 2041-1723
DOI: 10.1038/s41467-024-50948-z
Popis: Abstract Circumventing the issues of conventional stereocomplexation of preformed polymers, herein, we synthesize two enantiopure polymers of opposite chirality simultaneously and in situ as their 1:1 stereocomplex via topochemical polymerization. We design and synthesize an inositol-based achiral monomer for topochemical ene-azide cycloaddition (TEAC) polymerization. In the crystal, the monomer exhibits conformational enantiomerism, and its conformational enantiomers are self-sorted in an arrangement for TEAC polymerization to yield two enantiopure polymers of opposite chirality. Upon heating the monomer crystals, each self-sorted set of conformational enantiomers undergoes regio- and stereospecific polymerization in a single-crystal-to-single-crystal fashion, generating two 1, 4-triazolinyl-linked polymers of opposite chirality simultaneously. The new chiral carbons in all the triazoline rings of a particular polymer chain have the same absolute configuration. These homochiral polymer strands align parallelly, forming a layer, and such enantiopure layers of opposite chirality stack alternately, forming a perfect 1:1 stereocomplex, which we confirmed using single-crystal XRD analysis.
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