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Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross‐Linking
Author(s) -
Van Herck Niels,
Maes Diederick,
Unal Kamil,
Guerre Marc,
Winne Johan M.,
Du Prez Filip E.
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.201912902
Subject(s) - covalent bond , thiol , thioacetal , chemistry , dynamic covalent chemistry , alkyne , molecule , polymer , relaxation (psychology) , click chemistry , linker , combinatorial chemistry , computational chemistry , organic chemistry , computer science , catalysis , acetal , supramolecular chemistry , psychology , social psychology , operating system
The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker.