RT Journal Article
T1 Dynamic Axial-to-Helical Communication Mechanism in Poly[(allenylethynylenephenylene)acetylene]s under External Stimuli
A1 Lago Silva, María
A1 Cid, María Magdalena
A1 Quiñoá Cabana, Emilio
A1 Freire Iribarne, Félix Manuel
K1 Allenes
K1 Axial Chirality
K1 Helix Inversion
K1 Poly(phenylacetylene)s
K1 Stimuli-Responsive
AB Helix 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 polymers
PB Wiley
SN 1433-7851
YR 2023
FD 2023
LK http://hdl.handle.net/10347/30782
UL http://hdl.handle.net/10347/30782
LA eng
NO Lago-Silva, M., Cid, M. M., Quiñoá, E., Freire, F., Angew. Chem. Int. Ed. 2023, e202303329
NO We thank financial support from AEI (PID2019-109733GB-I00, PID2021-128057NB-I00), and Xunta de Galicia (ED431C 2022/21, Centro Singular de Investigación de Galicia acreditación 2019–2022, ED431G 2019/03 and the European Regional Development Fund (ERDF). ML also thanks Xunta de Galicia for a predoctoral contract. We are also thankful for Servicio de Nanotecnología y Análisis de Superficies (CACTI-CINBIO, UVigo) the use of the RIAIDT-USC analytical facilities and CESGA for cpu time
DS Minerva
RD 24 abr 2026