RT Journal Article
T1 Sequential Induction of Chirality in Helical Polymers: From the Stereocenter to the Achiral Solvent
A1 Nieto-Ortega, Belén
A1 Rodríguez Riego, Rafael
A1 Medina, Samara
A1 Quiñoá Cabana, Emilio
A1 Riguera Vega, Ricardo
A1 Casado, Juan
A1 Freire Iribarne, Félix Manuel
A1 Ramírez, Francisco Javier
AB Several steps of chiral induction have been detected in poly(phenylacetylene)s among their different hierarchical levels of chirality by vibrational circular dichroism, namely, (i) from the stereogenic centers to the innermost polyacetylene helical covalent backbone (helixint), (ii) from this to the external helix (helixext) formed by the side phenyl pendants that form a complementary helix or counter-helix, and (iii) from this pendant helix to the helical solvation sphere (helixsolv.), the last one being observed along this work. The pendant to polyene backbone chiral induction determines the helical structure adopted by the polymer and therefore the solvation helix. This helical structure is promoted by two mechanisms: steric effects and hydrogen bonding. An important finding concerns the demonstration by VCD of how an achiral solvent becomes chirally organized owing to the template effect of the covalent polymer helices, an effect that is silent to other structural techniques such as ECD or AFM and that hence significantly broadens the scope of these previous analyses
PB American Chemical Society
YR 2018
FD 2018-04-13
LK http://hdl.handle.net/10347/18883
UL http://hdl.handle.net/10347/18883
LA eng
NO Nieto-Ortega, B., Rodríguez, R., Medina, S., Quiñoá, E., Riguera, R., & Casado, J. et al. (2018). Sequential Induction of Chirality in Helical Polymers: From the Stereocenter to the Achiral Solvent. The Journal Of Physical Chemistry Letters, 9(9), 2266-2270. doi: 10.1021/acs.jpclett.8b00519
NO This is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of the Physical Chemistry Letters, Copyright © 2018 American Chemical Society after peer review and technical edityng by the publisher. To access the final edited and published work see: https://pubs.acs.org/doi/10.1021/acs.jpclett.8b00519
NO Financial support from Ministerio de Ciencia e Innovación [CTQ2014-61470-EXP, CTQ2015-69391-P, FPI (R. Rodríguez), FPU (S. Medina), Juan de la Cierva postdoctoral Fellowship FJCI-2015-23531 (B.Nieto-Ortega)], Xunta de Galicia (GRC2014/040, Centro singular deinvestigación de Galicia accreditation 2016-2019, ED431G/09) and the European RegionalDevelopment Fund (ERDF) is gratefully acknowledged
DS Minerva
RD 23 abr 2026