Conjugated Polymers That Respond to Oxidation with Increased Emission
Thioether-containing poly(para-phenylene-ethynylene) (PPE) copolymers show a strong fluorescence turn-on response when exposed to oxidants in solution as a result of the selective conversion of thioether substituents into sulfoxides and sulfones. We propose that the increase in fluorescence quantum...
| Main Authors: | , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2012
|
| Online Access: | http://hdl.handle.net/1721.1/74229 |
| _version_ | 1826202739911163904 |
|---|---|
| author | Swager, Timothy Manning Dane, Eric L. King, Sarah B. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Swager, Timothy Manning Dane, Eric L. King, Sarah B. |
| author_sort | Swager, Timothy Manning |
| collection | MIT |
| description | Thioether-containing poly(para-phenylene-ethynylene) (PPE) copolymers show a strong fluorescence turn-on response when exposed to oxidants in solution as a result of the selective conversion of thioether substituents into sulfoxides and sulfones. We propose that the increase in fluorescence quantum yield (Φ[subscript F]) upon oxidation is the result of both an increase in the rate of fluorescence (k[subscript F]), as a result of greater spatial overlap of the frontier molecular orbitals in the oxidized materials, and an increase in the fluorescence lifetime (τ[subscript F]), due to a decrease in the rate of nonradiative decay. Contrary to established literature, the reported sulfoxides do not always act as fluorescence quenchers. The oxidation is accompanied by spectral changes in the absorption and emission of the polymers, which are dramatic when oxidation causes the copolymer to acquire a donor−acceptor interaction. The oxidized polymers have high fluorescence quantum yields in the solid state, with some having increased photostability. A turn-on fluorescence response to hydrogen peroxide in organic solvents in the presence of an oxidation catalyst indicates the potential of thioether-containing materials for oxidant sensing. The reported polymers show promise as new materials in applications where photostability is important, where tunability of emission across the visible spectrum is desired, and where efficient emission is an advantage. |
| first_indexed | 2024-09-23T12:16:48Z |
| format | Article |
| id | mit-1721.1/74229 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T12:16:48Z |
| publishDate | 2012 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/742292022-10-01T08:51:07Z Conjugated Polymers That Respond to Oxidation with Increased Emission Swager, Timothy Manning Dane, Eric L. King, Sarah B. Massachusetts Institute of Technology. Department of Chemistry Swager, Timothy Manning Swager, Timothy Manning Dane, Eric L. King, Sarah B. Thioether-containing poly(para-phenylene-ethynylene) (PPE) copolymers show a strong fluorescence turn-on response when exposed to oxidants in solution as a result of the selective conversion of thioether substituents into sulfoxides and sulfones. We propose that the increase in fluorescence quantum yield (Φ[subscript F]) upon oxidation is the result of both an increase in the rate of fluorescence (k[subscript F]), as a result of greater spatial overlap of the frontier molecular orbitals in the oxidized materials, and an increase in the fluorescence lifetime (τ[subscript F]), due to a decrease in the rate of nonradiative decay. Contrary to established literature, the reported sulfoxides do not always act as fluorescence quenchers. The oxidation is accompanied by spectral changes in the absorption and emission of the polymers, which are dramatic when oxidation causes the copolymer to acquire a donor−acceptor interaction. The oxidized polymers have high fluorescence quantum yields in the solid state, with some having increased photostability. A turn-on fluorescence response to hydrogen peroxide in organic solvents in the presence of an oxidation catalyst indicates the potential of thioether-containing materials for oxidant sensing. The reported polymers show promise as new materials in applications where photostability is important, where tunability of emission across the visible spectrum is desired, and where efficient emission is an advantage. 2012-10-24T17:39:47Z 2012-10-24T17:39:47Z 2010-05 2010-03 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/74229 Dane, Eric L., Sarah B. King, and Timothy M. Swager. “Conjugated Polymers That Respond to Oxidation with Increased Emission.” Journal of the American Chemical Society 132.22 (2010): 7758–7768. en_US http://dx.doi.org/ 10.1021/ja1019063 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Swager via Erja Kajosalo |
| spellingShingle | Swager, Timothy Manning Dane, Eric L. King, Sarah B. Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title | Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title_full | Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title_fullStr | Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title_full_unstemmed | Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title_short | Conjugated Polymers That Respond to Oxidation with Increased Emission |
| title_sort | conjugated polymers that respond to oxidation with increased emission |
| url | http://hdl.handle.net/1721.1/74229 |
| work_keys_str_mv | AT swagertimothymanning conjugatedpolymersthatrespondtooxidationwithincreasedemission AT daneericl conjugatedpolymersthatrespondtooxidationwithincreasedemission AT kingsarahb conjugatedpolymersthatrespondtooxidationwithincreasedemission |