Cargando…
Relation between Morphology and Chiroptical Properties in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT
[Image: see text] The electronic properties of conducting polymers are influenced by their micro- and macrostructural orders, which can be tailored by substituent modification. However, while the effect of substituents on conducting polymers is extensively investigated, chiral substituents are far l...
Autores principales: | , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2020
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7660938/ https://www.ncbi.nlm.nih.gov/pubmed/33191953 http://dx.doi.org/10.1021/acs.macromol.0c01731 |
_version_ | 1783609116521922560 |
---|---|
author | Amsallem, Dana Bedi, Anjan Tassinari, Francesco Gidron, Ori |
author_facet | Amsallem, Dana Bedi, Anjan Tassinari, Francesco Gidron, Ori |
author_sort | Amsallem, Dana |
collection | PubMed |
description | [Image: see text] The electronic properties of conducting polymers are influenced by their micro- and macrostructural orders, which can be tailored by substituent modification. However, while the effect of substituents on conducting polymers is extensively investigated, chiral substituents are far less studied. Furthermore, many chiral conducting polymers have regioirregular structures, which result in polymer films with inferior properties. In this work, we apply electronic circular dichroism (ECD) spectroscopy to study the morphological changes to the chiral polymers under different polymerization conditions. For this purpose, we investigated 3,4-ethylenedioxythiophene (EDOT) derivatives having two stereogenic centers on each monomer and bearing methyl or phenyl side groups (dimethyl-EDOT and diphenyl-EDOT, respectively). Polymerizing the enantiomerically pure monomers produces regioregular and stereoregular dimethyl-PEDOT and diphenyl-PEDOT, respectively. The effect of the electrolyte and solvent on polymer film morphology was studied using scanning electron microscopy (SEM) and ECD, showing a correlation between the polymer’s morphology and the chiroptical properties of its films. We found that, for diphenyl-PEDOT, the combination of perchlorate anion electrolyte and acetonitrile solvent resulted in a unique morphology characterized by significant intermolecular interactions. These interactions were clearly observable in the ECD spectra in the form of exciton couplings, whose presence was supported by TD-DFT calculations. A small enantiomeric excess was sufficient to induce very intense ECD signals, demonstrating chiral amplification in electropolymerized films. |
format | Online Article Text |
id | pubmed-7660938 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-76609382020-11-13 Relation between Morphology and Chiroptical Properties in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT Amsallem, Dana Bedi, Anjan Tassinari, Francesco Gidron, Ori Macromolecules [Image: see text] The electronic properties of conducting polymers are influenced by their micro- and macrostructural orders, which can be tailored by substituent modification. However, while the effect of substituents on conducting polymers is extensively investigated, chiral substituents are far less studied. Furthermore, many chiral conducting polymers have regioirregular structures, which result in polymer films with inferior properties. In this work, we apply electronic circular dichroism (ECD) spectroscopy to study the morphological changes to the chiral polymers under different polymerization conditions. For this purpose, we investigated 3,4-ethylenedioxythiophene (EDOT) derivatives having two stereogenic centers on each monomer and bearing methyl or phenyl side groups (dimethyl-EDOT and diphenyl-EDOT, respectively). Polymerizing the enantiomerically pure monomers produces regioregular and stereoregular dimethyl-PEDOT and diphenyl-PEDOT, respectively. The effect of the electrolyte and solvent on polymer film morphology was studied using scanning electron microscopy (SEM) and ECD, showing a correlation between the polymer’s morphology and the chiroptical properties of its films. We found that, for diphenyl-PEDOT, the combination of perchlorate anion electrolyte and acetonitrile solvent resulted in a unique morphology characterized by significant intermolecular interactions. These interactions were clearly observable in the ECD spectra in the form of exciton couplings, whose presence was supported by TD-DFT calculations. A small enantiomeric excess was sufficient to induce very intense ECD signals, demonstrating chiral amplification in electropolymerized films. American Chemical Society 2020-10-22 2020-11-10 /pmc/articles/PMC7660938/ /pubmed/33191953 http://dx.doi.org/10.1021/acs.macromol.0c01731 Text en © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Amsallem, Dana Bedi, Anjan Tassinari, Francesco Gidron, Ori Relation between Morphology and Chiroptical Properties in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title | Relation between Morphology and Chiroptical Properties
in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title_full | Relation between Morphology and Chiroptical Properties
in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title_fullStr | Relation between Morphology and Chiroptical Properties
in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title_full_unstemmed | Relation between Morphology and Chiroptical Properties
in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title_short | Relation between Morphology and Chiroptical Properties
in Chiral Conducting Polymer Films: A Case Study in Chiral PEDOT |
title_sort | relation between morphology and chiroptical properties
in chiral conducting polymer films: a case study in chiral pedot |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7660938/ https://www.ncbi.nlm.nih.gov/pubmed/33191953 http://dx.doi.org/10.1021/acs.macromol.0c01731 |
work_keys_str_mv | AT amsallemdana relationbetweenmorphologyandchiropticalpropertiesinchiralconductingpolymerfilmsacasestudyinchiralpedot AT bedianjan relationbetweenmorphologyandchiropticalpropertiesinchiralconductingpolymerfilmsacasestudyinchiralpedot AT tassinarifrancesco relationbetweenmorphologyandchiropticalpropertiesinchiralconductingpolymerfilmsacasestudyinchiralpedot AT gidronori relationbetweenmorphologyandchiropticalpropertiesinchiralconductingpolymerfilmsacasestudyinchiralpedot |