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dc.contributor.authorArias, Sandra
dc.contributor.authorRodríguez Riego, Rafael
dc.contributor.authorRiguera Vega, Ricardo
dc.contributor.authorQuiñoá Cabana, Emilio
dc.contributor.authorFreire Iribarne, Félix Manuel
dc.date.accessioned2018-01-26T11:44:37Z
dc.date.available2019-12-14T02:00:10Z
dc.date.issued2017-12-14
dc.identifier.citationArias, S., Rodríguez, R., Quiñoá, E., Riguera, R., & Freire, F. (2018). Chiral Coalition in Helical Sense Enhancement of Copolymers: The Role of the Absolute Configuration of Comonomers. Journal Of The American Chemical Society, 140(2), 667-674. http://dx.doi.org/10.1021/jacs.7b09965
dc.identifier.issn0002-7863
dc.identifier.urihttp://hdl.handle.net/10347/16391
dc.descriptionNOTICE: This is the peer reviewed version of the following article: Arias, S.; Rodríguez, R., Quiñoá, E.; Riguera, R.; Freire, F.. Chiral Coalition in Helical Sense Enhancement of Copolymers: the Role of the Absolute Configuration of Comonomers Promoting the Helical Scaffold. J. Am. Chem. Soc. 2018, 140, 667-674. This article may be used for noncommercial purposes in accordance with ACS Terms and Conditions for self-archiving
dc.description.abstractBoth the role of the absolute configuration and the tendency of a chiral monomer to promote a certain helical scaffold in a polyphenylacetylene (PPA) —that depends on the conformational composition at the pendant group— have been evaluated to study the communication between two chiral monomers within a copolymer chain. 19 different PPA copolymer series —47 copolymers altogether— were prepared to explore the existence of a chiral to chiral communication mechanism in helical copolymers. From the data obtained, we found that communication between two different chiral monomers within a copolymer chain emerge when the two monomers exhibit two special features: (a) a different conformational composition —one chiral monomer must exist in a single low energy conformation ("chiral Sergeant") and the other must present an equilibrium between two different conformers ("chiral Soldier")—, and (b) both chiral monomers must promote a similar scaffold in the PPA, either cis-cisoidal or cis-transoidal. In the selected systems, the chiral Soldier includes the 4-ethynylanilide (para position) of either (R)- or (S)-2-methoxy-2-phenylacetic acid [(R)- or (S)-1], pendants characterized by their conformational flexibility once polymerized (equilibrium between synperiplanar and antiperiplanar conformations). The chiral Sergeant contains the same chiral groups but linked to the backbone in meta position [3-ethynylanilide of (R)- or (S)-2-methoxy-2-phenylacetic acid, (R)- or (S)-2] and is selected on the basis of its restricted antiperiplanar conformation. Incorporation of a very small amount (1%) of the Sergeant [either (R)- or (S)-2] to a chain composed just by the Soldier transforms the originally axially racemic chain into a helix with strong sense preference (either M or P) that is determined by the absolute configuration of the Soldier. For instance, both poly-[(R)-10.9-co-(R)-20.1] and poly-[(R)-10.9-co-(S)-20.1] adopt M helical structures due to the absolute configuration of the soldier, although the extent of the chiral amplification induced by the Sergeant is different as a consequence of a different communication mechanism between the (R)-Sergeant/(R)-Soldier and the (S)-Sergeant/(R)-Soldier
dc.description.sponsorshipWe thank the Ministerio de Ciencia e Innovacion ([CTQ2014-61470-EXP, CTQ2015-70519-P, FPI ́ (R.R.)], Fundacion Gil Da ́ vila fellowship (S.A.), Xunta de Galicia (Centro Singular de Investigación de Galicia accreditation 2016-2019, GRC2014/040), and the European Union (European Regional Development Fund-ERDF) for financial support
dc.language.isoeng
dc.publisherAmerican Chemistry Society
dc.relationinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2014-61470-EXP/ES/CATALIZADORES POLIMERICOS CON QUIRALIDAD REVERSIBLE
dc.relationinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2015-70519-P/ES/ATERIALES QUIROPTICOS MODULABLES A PARTIR DE POLIMEROS INTELIGENTES
dc.rights© American Chemical Society
dc.subjectChiral Communication
dc.subjectHelical Polymers
dc.subjectPoly(phenylacetylene)s
dc.subjectChiral Conflict
dc.subjectSergeants and Soldiers effect
dc.titleChiral Coalition in Helical Sense Enhancement of Copolymers: The Role of the Absolute Configuration of Comonomers
dc.typeinfo:eu-repo/semantics/article
dc.identifier.DOI10.1021/jacs.7b09965
dc.relation.publisherversionhttps://doi.org/10.1021/jacs.7b09965
dc.type.versioninfo:eu-repo/semantics/acceptedVersion
dc.identifier.e-issn1520-5126
dc.rights.accessrightsinfo:eu-repo/semantics/openAccess
dc.contributor.affiliationUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
dc.contributor.affiliationUniversidade de Santiago de Compostela. Departamento de Química Orgánica
dc.description.peerreviewedSI


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