Dissymmetric Chiral Poly(diphenylacetylene)s: Secondary Structure Elucidation and Dynamic Luminescence

Freire, Félix; Tarrío, Juan José; Rodríguez, Rafael; Fernández, Berta; Quiñoá, Emilio

doi:10.1002/ange.202115070

Cited by 7 publications

(1 citation statement)

References 128 publications

(110 reference statements)

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“…In consequence, a large variety of non‐natural foldamers and helical polymers have been studied during the last decades. In the special case of helical polymers, families such as poly(isocyanide)s, 3 poly(isocyanate)s, 4 poly(diphenylacetylene)s, 5,6 or polyacetylenes, 7,8 among others, provide a large variety of helical scaffolds with different static/dynamic, which properties find applications in different fields such as chiral materials asymmetric catalysis, 9–13 chiral recognition, 14,15 circular polarized luminescence (CPL) sources, 5,6,15,16 chiroptical switches, 17,18 or chiral stationary phases for high performance liquid chromatography (HPLC) among others 19–21 . To be functional, these helical polymers must adopt macromolecular helical structures with screw sense excess.…”

Section: Introductionmentioning

confidence: 99%

Diastereomeric multi‐chiral pendant groups: Their key role in stimuli‐responsive polymeric responses

et al. 2023

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Chiral information transmission in helical polymers bearing multi-chiral pendant groups is usually determined by the absolute configuration of the first chiral center. The second chiral residue usually has low-to-null influence in the macromolecular handedness of the polymer, due to its remote position respect to the polyene main chain. Here, we demonstrate how the stimuli responsive properties of diastereomeric polymers, obtained by changing the absolute configuration of the second chiral center, are different due to the unlike properties of diastereoisomers.

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Section: Introductionmentioning

confidence: 99%

Diastereomeric multi‐chiral pendant groups: Their key role in stimuli‐responsive polymeric responses

et al. 2023

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Photostability and Dynamic Helical Behavior in Chiral Poly(phenylacetylene)s with a Preferred Screw‐Sense

et al. 2022

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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.

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Full Control of the Chiral Overpass Effect in Helical Polymers: P/M Screw Sense Induction by Remote Chiral Centers After Bypassing the First Chiral Residue

et al. 2022

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In helical polymers, helical sense induction is usually commanded by teleinduction mechanism, where the largest substituent of the chiral residue directly attached to the main chain is the one that commands the helical sense. In this work, different helical structures with different helical senses are induced in a helical polymer [poly-(phenylacetylene)] when the conformational composition of two different dihedral angles of a pendant group with more than two chiral residues is tamed. Thus, while the dihedral angle at chiral residue 1 [(R)-or (S)-alanine], attached to the backbone, produces an extended or bent conformation in the pendant resulting in two scaffolds with different stretching degree, the second dihedral angle at chiral residue 2 [(R)-or (S)-methoxyphenylacetamide] places the substituents of this chiral center in a different spatial orientation, originating opposite helical senses at the polymer that are induced through a total control of the "chiral overpass effect".

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Dissymmetric Chiral Poly(diphenylacetylene)s: Secondary Structure Elucidation and Dynamic Luminescence

Cited by 7 publications

References 128 publications

Diastereomeric multi‐chiral pendant groups: Their key role in stimuli‐responsive polymeric responses

Diastereomeric multi‐chiral pendant groups: Their key role in stimuli‐responsive polymeric responses

Photostability and Dynamic Helical Behavior in Chiral Poly(phenylacetylene)s with a Preferred Screw‐Sense

Full Control of the Chiral Overpass Effect in Helical Polymers: P/M Screw Sense Induction by Remote Chiral Centers After Bypassing the First Chiral Residue

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