Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

Handle URI:
http://hdl.handle.net/10754/617303
Title:
Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization
Authors:
Vidal, Fernando; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Chen, Eugene Y.-X.
Abstract:
The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization 2016 Journal of the American Chemical Society
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
7-Jul-2016
DOI:
10.1021/jacs.6b04064
Type:
Article
ISSN:
0002-7863; 1520-5126
Sponsors:
This work was supported by the US National Science Foundation (NSF- 1300267) for the study carried out at Colorado State University. L. Cavallo thanks the HPC team of Enea (www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy. We thank Boulder Scientific Co. for the research gifts of B(C6F5)3 and [Ph3C][B(C6F5)4].
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.6b04064
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Full metadata record

DC FieldValue Language
dc.contributor.authorVidal, Fernandoen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorChen, Eugene Y.-X.en
dc.date.accessioned2016-07-21T10:07:50Z-
dc.date.available2016-07-21T10:07:50Z-
dc.date.issued2016-07-07-
dc.identifier.citationRobust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization 2016 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863-
dc.identifier.issn1520-5126-
dc.identifier.doi10.1021/jacs.6b04064-
dc.identifier.urihttp://hdl.handle.net/10754/617303-
dc.description.abstractThe successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.en
dc.description.sponsorshipThis work was supported by the US National Science Foundation (NSF- 1300267) for the study carried out at Colorado State University. L. Cavallo thanks the HPC team of Enea (www.enea.it) for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) in Portici, Italy. We thank Boulder Scientific Co. for the research gifts of B(C6F5)3 and [Ph3C][B(C6F5)4].en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.6b04064en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.6b04064.en
dc.titleRobust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerizationen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USAen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, I-84084, Fisciano, Italyen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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