Raman Optical Activity (ROA) as a New Tool to Elucidate the Helical Structure of Poly(phenylacetylene)s
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Title: | Raman Optical Activity (ROA) as a New Tool to Elucidate the Helical Structure of Poly(phenylacetylene)s |
Author: | Palomo, Luis Rodríguez Riego, Rafael Medina, Samara Quiñoá Cabana, Emilio Casado, Juan Freire Iribarne, Félix Manuel Ramírez, Francisco Javier |
Affiliation: | Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares Universidade de Santiago de Compostela. Departamento de Química Orgánica |
Subject: | Circular Dichroism | Helical Polymers | Helical Sense | Poly(phenylacetylene)s | Raman Optical Activity | |
Date of Issue: | 2020 |
Publisher: | Wiley |
Citation: | L. Palomo, R. Rodríguez, S. Medina, E. Quiñoá, J. Casado, F. Freire, F. J. Ramírez, Angew. Chem. Int. Ed. 2020, 59, 9080 |
Abstract: | Poly(phenylacetylene)s are a family of helical polymers constituted by conjugated double bonds. Raman spectra of these polymers show a structural fingerprint of the polyene backbone which, in combination with its helical orientation, makes them good candidates to be studied by Raman optical activity (ROA). Four different well‐known poly(phenylacetylene)s adopting different scaffolds and ten different helical senses have been prepared. Raman and ROA spectra were recorded and allowed to establish ROA‐spectrum/helical‐sense relationships: a left/right‐handed orientation of the polyene backbone (Mhelix/Phelix) produces a triplet of positive/negative ROA bands. Raman and ROA spectra of each polymer exhibited the same profile, and the sign of the ROA spectrum was opposite to the lowest‐energy electronic circular dichroism (ECD) band, indicating a resonance effect. Resonance ROA appears then as an indicator of the helical sense of poly(phenylacetylene)s, especially for those with an extra Cotton band in the ECD spectrum, where a wrong helical sense is assigned based on ECD, while ROA alerts of this misassignment |
Description: | This is the peer reviewed version of the following article: L. Palomo, R. Rodríguez, S. Medina, E. Quiñoá, J. Casado, F. Freire, F. J. Ramírez, Angew. Chem. Int. Ed. 2020, 59, 9080, which has been published in final form at https://doi.org/10.1002/anie.202000651. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions |
Publisher version: | https://doi.org/10.1002/anie.202000651 |
URI: | http://hdl.handle.net/10347/23378 |
DOI: | 10.1002/anie.202000651 |
ISSN: | 1433-7851 |
E-ISSN: | 1521-3773 |
Rights: | © 2020 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for self-archiving |
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