Predicting the Helical Sense of Poly(phenylacetylene)s from their Electron Circular Dichroism Spectra
Corresponding Author
Prof. Berta Fernández
Departmento de Química Física, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Search for more papers by this authorRafael Rodríguez
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorProf. Antonio Rizzo
Instituto per i Processi Chimico-Fisici (IPCF), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Pisa, 56124 Pisa, Italy
Search for more papers by this authorProf. Emilio Quiñoá
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorProf. Ricardo Riguera
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorCorresponding Author
Prof. Félix Freire
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorCorresponding Author
Prof. Berta Fernández
Departmento de Química Física, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Search for more papers by this authorRafael Rodríguez
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorProf. Antonio Rizzo
Instituto per i Processi Chimico-Fisici (IPCF), Consiglio Nazionale delle Ricerche (CNR), Area della Ricerca di Pisa, 56124 Pisa, Italy
Search for more papers by this authorProf. Emilio Quiñoá
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorProf. Ricardo Riguera
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorCorresponding Author
Prof. Félix Freire
Centro Singular de investigación en Química Biolóxica e, Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Jenaro de la Fuente s/n (Edificio CiQUS), Santiago de Compostela, Spain
Search for more papers by this authorGraphical Abstract
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.
Abstract
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.
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