Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization
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Meshanism of....Angewandte Chemie Intl Edit - 2022 - Chen - Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer.pdf
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Accepted manuscript
Embargo End Date:
2023-02-08
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ArticleAuthors
Chen, Eugene Y.-X.McGraw, Michael L.
Reilly, Liam T.
Clarke, Ryan W.
Cavallo, Luigi

Falivene, Laura
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2022-02-08Embargo End Date
2023-02-08Submitted Date
2021-11-30Permanent link to this record
http://hdl.handle.net/10754/675496
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In typical cyclic polymer synthesis via ring-closure, chain growth and cyclization events are competing with each other, thus affording cyclic polymers with uncontrolled molecular weight or ring size and high dispersity. Here we uncover a mechanism by which Lewis pair polymerization (LPP) operates on polar vinyl monomers that allows the control of where and when cyclization takes place, thereby achieving spatial and temporal control to afford precision cyclic vinyl polymers or block copolymers with predictable molecular weight and low dispersity (~1.03). A combined experimental and theoretical study demonstrates that cyclization occurs only after all monomers have been consumed (when) via conjugate addition of the propagating chain end to the specific site of the initiating chain end (where), allowing the cyclic polymer formation steps to be regulated and executed with precision in space and time.Citation
Chen, McGraw, M. L., Reilly, L. T., Clarke, R. W., Cavallo, L., & Falivene, L. (2022). Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization. Angewandte Chemie International Edition. Portico. https://doi.org/10.1002/anie.202116303Sponsors
We gratefully acknowledge support by the U.S. National Science Foundation (NSF-1904962) for the work by MLM and LTR, and the U.S. Army Research Office (W911NF1810435) for the work by RWC. We thank Dr. Roy Geiss for his expertise and assistance with acquiring TEM images.Publisher
WileyAdditional Links
https://onlinelibrary.wiley.com/doi/10.1002/anie.202116303ae974a485f413a2113503eed53cd6c53
10.1002/anie.202116303