Predicting the Helical Sense of Poly(phenylacetylene)s from their Electron Circular Dichroism Spectra

The calculated ECD spectrum (time‐dependent density functional theory TD‐DFT) for small oligomers of polyphenylacetylenes (PPAs) show a very good match with the experimental spectra of the PPA polymers, particularly with the first Cotton band associated to the helical sense of the internal polyenic...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-03, Vol.57 (14), p.3666-3670
Main Authors: Fernández, Berta, Rodríguez, Rafael, Rizzo, Antonio, Quiñoá, Emilio, Riguera, Ricardo, Freire, Félix
Format: Article
Language:English
Subjects:
chirality
Circular dichroism
Cotton
density functional calculations
Density functional theory
helical sense
Oligomers
Polymers
Polyphenylacetylene
Predictions
Spectra
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Summary:The calculated ECD spectrum (time‐dependent density functional theory TD‐DFT) for small oligomers of polyphenylacetylenes (PPAs) show a very good match with the experimental spectra of the PPA polymers, particularly with the first Cotton band associated to the helical sense of the internal polyenic backbone. This has been proven with a series of PPAs representative of cis‐cisoidal, cis‐transoidal, compressed and stretched polyene backbones, with identical or opposite internal/external rotational senses and allows the prediction of the helical sense of the internal helix of a PPA directly from its CD spectra. Helical polymers: A computational methodology on poly(phenylacetylene) oligomers allows assignment of the helical sense of polyene backbones based on their electron circular dichroism (EDC) signature. The calculated ECD spectrum for small oligomers of polyphenylacetylenes (PPAs) shows a very good match with the experimental spectra of the PPA polymers.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201713164