Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts
The helical sense and elongation of a helical polymer that bears the 4-ethynylanilide of (R)-α‑methoxy-α-phenylacetic acid [m-(R)-1] can be tuned by the action of the two components of tetraalkylammonium-anion salts. Thus, while the supramolecular PPA-anilide/anion interaction creates a chiroptical...
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Elsevier
2021-08-01
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| Series: | Giant |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666542521000242 |
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| author | Seila Leiras Esteban Suárez-Picado Emilio Quiñoá Ricardo Riguera Félix Freire |
| author_facet | Seila Leiras Esteban Suárez-Picado Emilio Quiñoá Ricardo Riguera Félix Freire |
| author_sort | Seila Leiras |
| collection | DOAJ |
| description | The helical sense and elongation of a helical polymer that bears the 4-ethynylanilide of (R)-α‑methoxy-α-phenylacetic acid [m-(R)-1] can be tuned by the action of the two components of tetraalkylammonium-anion salts. Thus, while the supramolecular PPA-anilide/anion interaction creates a chiroptical switch, inducing either P or M helical senses in the poly(phenylacetylene) (PPA) depending on the nature of the anion —P helix: fluoride (F−) or cyanide (CN−); M helix: acetate (OAc−), benzoate (OBz−) or azide (N3−)—, deprotonation of the anilide group by these anions in dry conditions makes it possible to play with the elongation of the PPA, depending on the size of the tetraalkylammonium group, which results in a colorimetric switch. Thus, a color change from yellow to deep red is obtained by deprotonation of the anilide group when a tetraabutylammonium salt is used, while yellow/light-red and yellow/orange color changes are obtained when the size of the tetraalkylammonium group is reduced. Structural and mechanistic studies confirm that the color change occurs when the counterion accommodates itself close to the pendant group once the anilide hydrogen is removed. This PPA/tetraalkylammonium association is responsible of elongation changes in the PPA and therefore on the conjugation of the polyene backbone that is accompanied with color changes. Moreover, this colorimetric switch also operates in the solid state and can be switched in a vacuum/air moisture cycle. |
| first_indexed | 2024-12-13T19:47:17Z |
| format | Article |
| id | doaj.art-5cd9bd61a17e441bb8db1ff591ee22cd |
| institution | Directory Open Access Journal |
| issn | 2666-5425 |
| language | English |
| last_indexed | 2024-12-13T19:47:17Z |
| publishDate | 2021-08-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Giant |
| spelling | doaj.art-5cd9bd61a17e441bb8db1ff591ee22cd2022-12-21T23:33:32ZengElsevierGiant2666-54252021-08-017100068Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion saltsSeila Leiras0Esteban Suárez-Picado1Emilio Quiñoá2Ricardo Riguera3Félix Freire4Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica. Universidade de Santiago de Compostela, 15782 Santiago de Compostela, SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica. Universidade de Santiago de Compostela, 15782 Santiago de Compostela, SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica. Universidade de Santiago de Compostela, 15782 Santiago de Compostela, SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica. Universidade de Santiago de Compostela, 15782 Santiago de Compostela, SpainCorrespondign author.; Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica. Universidade de Santiago de Compostela, 15782 Santiago de Compostela, SpainThe helical sense and elongation of a helical polymer that bears the 4-ethynylanilide of (R)-α‑methoxy-α-phenylacetic acid [m-(R)-1] can be tuned by the action of the two components of tetraalkylammonium-anion salts. Thus, while the supramolecular PPA-anilide/anion interaction creates a chiroptical switch, inducing either P or M helical senses in the poly(phenylacetylene) (PPA) depending on the nature of the anion —P helix: fluoride (F−) or cyanide (CN−); M helix: acetate (OAc−), benzoate (OBz−) or azide (N3−)—, deprotonation of the anilide group by these anions in dry conditions makes it possible to play with the elongation of the PPA, depending on the size of the tetraalkylammonium group, which results in a colorimetric switch. Thus, a color change from yellow to deep red is obtained by deprotonation of the anilide group when a tetraabutylammonium salt is used, while yellow/light-red and yellow/orange color changes are obtained when the size of the tetraalkylammonium group is reduced. Structural and mechanistic studies confirm that the color change occurs when the counterion accommodates itself close to the pendant group once the anilide hydrogen is removed. This PPA/tetraalkylammonium association is responsible of elongation changes in the PPA and therefore on the conjugation of the polyene backbone that is accompanied with color changes. Moreover, this colorimetric switch also operates in the solid state and can be switched in a vacuum/air moisture cycle.http://www.sciencedirect.com/science/article/pii/S2666542521000242Size effectStretching degreePoly(phenylacetylene)sChirality, helix |
| spellingShingle | Seila Leiras Esteban Suárez-Picado Emilio Quiñoá Ricardo Riguera Félix Freire Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts Giant Size effect Stretching degree Poly(phenylacetylene)s Chirality, helix |
| title | Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts |
| title_full | Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts |
| title_fullStr | Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts |
| title_full_unstemmed | Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts |
| title_short | Tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium-anion salts |
| title_sort | tuning the helical sense and elongation of polymers through the combined action of the two components of tetraalkylammonium anion salts |
| topic | Size effect Stretching degree Poly(phenylacetylene)s Chirality, helix |
| url | http://www.sciencedirect.com/science/article/pii/S2666542521000242 |
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