Lago Silva, MaríaCid, María MagdalenaQuiñoá Cabana, EmilioFreire Iribarne, Félix Manuel2023-06-232023-06-232023Lago-Silva, M., Cid, M. M., Quiñoá, E., Freire, F., Angew. Chem. Int. Ed. 2023, e2023033291433-7851http://hdl.handle.net/10347/30782Helix inversion in chiral dynamic helical polymers is usually achieved by conformational changes at the pendant groups induced through external stimuli. Herein, a different mechanism of helix inversion in poly(phenylacetylene)s (PPAs) is presented, based on the activation/deactivation of supramolecular interactions. We prepared poly[(allenylethynylenephenylene)acetylene]s (PAEPAs) in which the pendant groups are conformationally locked chiral allenes. Therefore, their substituents are placed in specific spatial orientations. As a result, the screw sense of a PAEPA is fixed by the allenyl substituent with the optimal size/distance relationship to the backbone. This helical sense command can be surpassed by supramolecular interactions between another substituent on the allene and appropriate external stimuli, such as amines. So, a helix inversion occurs through a novel axial-to-helical communication mechanism, opening a new scenario for taming the helices of chiral dynamic helical polymerseng© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is noncommercial and no modifications or adaptations are madehttp://creativecommons.org/licenses/by-nc-nd/4.0/AllenesAxial ChiralityHelix InversionPoly(phenylacetylene)sStimuli-Responsivejournal article10.1002/anie.2023033291521-3773open access