Photostability and dynamic helical behavior in chiral poly(phenylacetylene)s with a preferred screw-sense

Helical polymers such as poly(phenylacetylene)s (PPAs) are interesting materials due to the possibility of tuning their helical scaffold (sense and elongation) once they have been prepared and by the presence of external stimuli. The main limitation in the application of PPAs is their poor photostab...

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Detalles Bibliográficos
Autores: Rey-Tarrío, Francisco, Guisán Ceinos, Santiago, Cuerva, Juan Manuel, Miguel, Delia, Ribagorda Lobera, María, Quiñoá, Emilio, Freire, Félix
Tipo de recurso: artículo
Fecha de publicación:2022
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/721008
Acceso en línea:http://hdl.handle.net/10486/721008
https://dx.doi.org/10.1002/anie.202207623
Access Level:acceso abierto
Palabra clave:Chiroptical properties
dynamic helices
helical structure
photostability
poly(phenylacetylene)s
Química
Descripción
Sumario:Helical polymers such as poly(phenylacetylene)s (PPAs) are interesting materials due to the possibility of tuning their helical scaffold (sense and elongation) once they have been prepared and by the presence of external stimuli. The main limitation in the application of PPAs is their poor photostability. These polymers degrade under visible light exposure through a photochemical electrocyclization process. In this work, it was demonstrated, through a selected example, how the photochemical degradation in PPAs is directly related to their dynamic helical behavior. Thus, while PPAs with dynamic helical structures show poor photostability under UV/Vis light exposure, poly-(R)-1, bearing an enantiopure sulfoxide group as pendant group and designed to have a quasi-static helical behavior, shows a large photostability due to the restricted conformational composition at the polyene backbone, needed to orient the conjugated double bonds prior to the photochemical electrocyclization process and the subsequent degradation of the material