Topochemical Syntheses of Polyarylopeptides Involving Large Molecular Motions: Frustrated Monomer Packing Leads to the Formation of Polymer Blends

Cijil Raju, Kozhukunnon Mridula, Nikitha Srinivasan, Sooraj Kunnikuruvan, Kana M. Sureshan

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

We report the topochemical syntheses of three polyarylopeptides, wherein triazolylphenyl group is integrated into the backbone of peptide chains. We synthesized three different monomers having azide and arylacetylene as end-groups from glycine, L-alanine and L-valine. We crystallized these monomers and the crystal structures of two of them were determined by single-crystal X-ray diffractometry. Due to the steric constraints, both of these monomers crystallized with two molecules, viz. conformers A and B, in the asymmetric unit. Consistently, in both cases, the A-conformers are antiparallelly π-stacked and B-conformers are parallelly slip-stacked, exploiting weak interactions. Though the arrangements of molecules in the pristine crystals were unsuitable for topochemical reaction, upon heating, they undergo large motion inside the crystal lattice to reach a transient reactive orientation and thereby the self-sorted conformer stacks react to give a blend of triazole-linked polyarylopeptides having two different linkages. Due to the large molecular motion inside crystals, the product phase loses its crystallinity.

Original languageEnglish
Article numbere202306504
JournalAngewandte Chemie - International Edition
Volume62
Issue number37
Early online date24 Jul 2023
DOIs
StatePublished - 11 Sep 2023
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2023 Wiley-VCH GmbH.

Funding

K.M.S. thanks ISRO for a research grant (ISRO/RES/3/861/19‐20). SK thanks the Department of Science and Technology (DST), India for the INSPIRE faculty fellowship. SK and NS thank IIT Madras and the Centre for Atomistic Modelling and Materials Design, IIT Madras for the high‐performance computing (HPC) facilities. K.M.S. thanks ISRO for a research grant (ISRO/RES/3/861/19-20). SK thanks the Department of Science and Technology (DST), India for the INSPIRE faculty fellowship. SK and NS thank IIT Madras and the Centre for Atomistic Modelling and Materials Design, IIT Madras for the high-performance computing (HPC) facilities.

FundersFunder number
Department of Science and Technology, Ministry of Science and Technology, India
Indian Institute of Technology Madras

    Keywords

    • Arylopeptide
    • Click Chemistry
    • Peptidomimetic
    • Polymerization
    • Topochemical Reaction

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