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Designed Synthesis of a 1D Polymer in Twist‐Stacked Topology via Single‐Crystal‐to‐Single‐Crystal Polymerization
Author(s) -
Athiyarath Vignesh,
Sureshan Kana M.
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202006758
Subject(s) - polymer , materials science , monomer , polymerization , topology (electrical circuits) , molecule , crystallography , thermal stability , single crystal , thermogravimetric analysis , polymer chemistry , chemistry , composite material , organic chemistry , mathematics , combinatorics
To synthesize a fully organic 1D polymer in a novel twist‐stacked topology, we designed a peptide monomer HC≡CCH 2 ‐NH‐Ile‐Leu‐N 3 , which crystallizes with its molecules H‐bonded along a six‐fold screw axis. These H‐bonded columns pack parallelly such that molecules arrange head‐to‐tail, forming linear non‐covalent chains in planes perpendicular to the screw axis. The chains arrange parallelly to form molecular layers which twist‐stack along the screw axis. Crystals of this monomer, on heating, undergo single‐crystal‐to‐single‐crystal (SCSC) topochemical azide–alkyne cycloaddition (TAAC) polymerization to yield an exclusively 1,4‐triazole‐linked polymer in a twist‐stacked layered topology. This topologically defined polymer shows better mechanical strength and thermal stability than its unordered form, as evidenced by nanoindentation studies and thermogravimetric analysis, respectively. This work illustrates the scope of topochemical polymerizations for synthesizing polymers in pre‐decided topologies.