Cobos Cabrera, Scarlet KatherineRodríguez Riego, RafaelDomarco Álvarez, OlayaFernández Rodríguez, BertaQuiñoá Cabana, EmilioRiguera Vega, RicardoFreire Iribarne, Félix Manuel2020-10-092021-04-142020Macromolecules 2020, 53, 8, 3182–31930024-9297http://hdl.handle.net/10347/23381This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © 2020 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see: https://doi.org/10.1021/acs.macromol.0c00085Preparation of helical structures à la carte by monomer design of dynamic helical polymers such as poly(phenylacetylene)s (PPAs) is a difficult task due to conformational freedom of the polyene backbone. Herein, we study the monomer/helical polymer scaffold relationship by preparation of two novel phenylacetylene monomer series substituted at the phenyl ring in ortho-, meta-, or para-positions with the two enantiomers of either α-hydroxy-α-phenylacetic acid (1) or α-chloro-α-phenylacetic acid (S-2) linked through an anilide bond. These monomers were further polymerized, and their secondary structure and dynamic behavior were analyzed. Compiling information from these studies and the structural data for other PPAs found in the literature, we can state that anilide linkages in para-substituted polymers tend to generate compressed cis-cisoidal polyene structures, which can be transformed into more elongated cis-transoidal ones by external stimuli, while benzamide linkages in para-substituted polymers form mainly cis-transoidal scaffolds. The macromolecular structure of PPAs is also largely affected by the aromatic substitution pattern, adopting more stretched scaffolds once the pendant group is placed in meta- or ortho-positions, due to the steric hindrance generated by placing this group closer to the backboneeng© 2020 American Chemical Society. This article may be used for non-commercial purposes in accordance with ACS Terms and Conditions for Use of Self-Archived VersionsMonomersChemical structureCarbonylsSolventsPolymersjournal article10.1021/acs.macromol.0c000851520-5835open access