Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane
Modification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has...
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| Format: | Article |
| Language: | English |
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Frontiers Media S.A.
2019-03-01
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| Series: | Frontiers in Chemistry |
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| Online Access: | https://www.frontiersin.org/article/10.3389/fchem.2019.00123/full |
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| author | Emmanuel Reichsöllner Adam Creamer Shengyu Cong Abby Casey Simon Eder Martin Heeney Florian Glöcklhofer Florian Glöcklhofer |
| author_facet | Emmanuel Reichsöllner Adam Creamer Shengyu Cong Abby Casey Simon Eder Martin Heeney Florian Glöcklhofer Florian Glöcklhofer |
| author_sort | Emmanuel Reichsöllner |
| collection | DOAJ |
| description | Modification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has not been studied for the modification of conjugated polymers used in organic electronics. Crucial questions regarding selectivity and reaction time waited to be addressed. Here, we show that the reaction is highly selective and complete within just a few minutes when using dimethyldioxirane (DMDO) for the oxidation of thioalkyl substituents attached to the well-investigated conjugated polymers poly(9-(1-octylnonyl)carbazole-alt-4,7-dithienylbenzothiadiazole) (PCDTBT) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The selectivity was confirmed by comparison with polymers obtained from pre-oxidized monomers and by control experiments using related polymers without thioalkyl substituents. Using DMDO, the oxidation yields acetone as the only side-product, which reduces the work-up to mere evaporation of solvents and excessive reagent. Our results show that this oxidation is an exciting method for the preparation of electron-deficient conjugated polymers. It may even allow the preparation of electron acceptors for solar cells directly from the electron donors. |
| first_indexed | 2024-12-12T09:03:33Z |
| format | Article |
| id | doaj.art-36d2b558fb334de5b45bb6bf950457ae |
| institution | Directory Open Access Journal |
| issn | 2296-2646 |
| language | English |
| last_indexed | 2024-12-12T09:03:33Z |
| publishDate | 2019-03-01 |
| publisher | Frontiers Media S.A. |
| record_format | Article |
| series | Frontiers in Chemistry |
| spelling | doaj.art-36d2b558fb334de5b45bb6bf950457ae2022-12-22T00:29:45ZengFrontiers Media S.A.Frontiers in Chemistry2296-26462019-03-01710.3389/fchem.2019.00123436857Fast and Selective Post-polymerization Modification of Conjugated Polymers Using DimethyldioxiraneEmmanuel Reichsöllner0Adam Creamer1Shengyu Cong2Abby Casey3Simon Eder4Martin Heeney5Florian Glöcklhofer6Florian Glöcklhofer7Institute of Applied Synthetic Chemistry, TU Wien, Vienna, AustriaDepartment of Chemistry and Centre for Plastic Electronics, Imperial College London, London, United KingdomDepartment of Chemistry and Centre for Plastic Electronics, Imperial College London, London, United KingdomDepartment of Chemistry and Centre for Plastic Electronics, Imperial College London, London, United KingdomInstitute of Applied Synthetic Chemistry, TU Wien, Vienna, AustriaDepartment of Chemistry and Centre for Plastic Electronics, Imperial College London, London, United KingdomInstitute of Applied Synthetic Chemistry, TU Wien, Vienna, AustriaDepartment of Chemistry and Centre for Plastic Electronics, Imperial College London, London, United KingdomModification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has not been studied for the modification of conjugated polymers used in organic electronics. Crucial questions regarding selectivity and reaction time waited to be addressed. Here, we show that the reaction is highly selective and complete within just a few minutes when using dimethyldioxirane (DMDO) for the oxidation of thioalkyl substituents attached to the well-investigated conjugated polymers poly(9-(1-octylnonyl)carbazole-alt-4,7-dithienylbenzothiadiazole) (PCDTBT) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The selectivity was confirmed by comparison with polymers obtained from pre-oxidized monomers and by control experiments using related polymers without thioalkyl substituents. Using DMDO, the oxidation yields acetone as the only side-product, which reduces the work-up to mere evaporation of solvents and excessive reagent. Our results show that this oxidation is an exciting method for the preparation of electron-deficient conjugated polymers. It may even allow the preparation of electron acceptors for solar cells directly from the electron donors.https://www.frontiersin.org/article/10.3389/fchem.2019.00123/fullorganic electronicsconjugated polymerspost-polymerization modificationoxidationsulfoxidesulfone |
| spellingShingle | Emmanuel Reichsöllner Adam Creamer Shengyu Cong Abby Casey Simon Eder Martin Heeney Florian Glöcklhofer Florian Glöcklhofer Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane Frontiers in Chemistry organic electronics conjugated polymers post-polymerization modification oxidation sulfoxide sulfone |
| title | Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane |
| title_full | Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane |
| title_fullStr | Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane |
| title_full_unstemmed | Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane |
| title_short | Fast and Selective Post-polymerization Modification of Conjugated Polymers Using Dimethyldioxirane |
| title_sort | fast and selective post polymerization modification of conjugated polymers using dimethyldioxirane |
| topic | organic electronics conjugated polymers post-polymerization modification oxidation sulfoxide sulfone |
| url | https://www.frontiersin.org/article/10.3389/fchem.2019.00123/full |
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