Redox Switchable Thianthrene Cavitands
A redox activated vase-to-kite conformational change is reported for a new resorcinarene-based cavitand appended with four quinoxaline-fused thianthrene units. In its neutral state, the thianthrene-containing cavitand was shown by 1H NMR to adopt a closed vase conformation. Upon oxidation the electr...
| Autores principales: | , , , |
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| Formato: | Artículo |
| Lenguaje: | en_US |
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Thieme Publishing Group
2018
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| Acceso en línea: | http://hdl.handle.net/1721.1/114719 https://orcid.org/0000-0002-2868-8682 |
| _version_ | 1826197219261284352 |
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| author | Bertani, Federico Dalcanale, Enrico Ong, Wen Jie Swager, Timothy M |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Bertani, Federico Dalcanale, Enrico Ong, Wen Jie Swager, Timothy M |
| author_sort | Bertani, Federico |
| collection | MIT |
| description | A redox activated vase-to-kite conformational change is reported for a new resorcinarene-based cavitand appended with four quinoxaline-fused thianthrene units. In its neutral state, the thianthrene-containing cavitand was shown by 1H NMR to adopt a closed vase conformation. Upon oxidation the electrostatic repulsion among the thianthrene radical cations promotes a kite conformation in the thianthrene-containing cavitand. The addition of acid produced a shoulder feature below 300 nm in the cavitand’s UV-Vis spectrum that we have assigned to the vase-to-kite conformation change. UV-Vis spectroelectrochemical studies of the cavitand revealed a development of a similar shoulder peak consistent with the oxidation-induced vase-to-kite conformation change. To support that the shoulder peak is diagnostic for a vase-to-kite conformation change, a model molecule constituting a single quinoxaline wall of the cavitand was synthesized and studied. As expected UV-Vis spectroelectrochemical studies of the cavitand arm did not display a shoulder peak below 300 nm. The oxidation-induced vase-to-kite conformation is further confirmed by the distinctive upfield shift in 1H chemical shift of the methine signal. Key words: redox active, thianthrene, resorcinarene cavitands, electrochemical switching, conformation change |
| first_indexed | 2024-09-23T10:44:19Z |
| format | Article |
| id | mit-1721.1/114719 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T10:44:19Z |
| publishDate | 2018 |
| publisher | Thieme Publishing Group |
| record_format | dspace |
| spelling | mit-1721.1/1147192022-09-30T22:40:06Z Redox Switchable Thianthrene Cavitands Bertani, Federico Dalcanale, Enrico Ong, Wen Jie Swager, Timothy M Massachusetts Institute of Technology. Department of Chemistry Swager, Timothy M Ong, Wen Jie Swager, Timothy M A redox activated vase-to-kite conformational change is reported for a new resorcinarene-based cavitand appended with four quinoxaline-fused thianthrene units. In its neutral state, the thianthrene-containing cavitand was shown by 1H NMR to adopt a closed vase conformation. Upon oxidation the electrostatic repulsion among the thianthrene radical cations promotes a kite conformation in the thianthrene-containing cavitand. The addition of acid produced a shoulder feature below 300 nm in the cavitand’s UV-Vis spectrum that we have assigned to the vase-to-kite conformation change. UV-Vis spectroelectrochemical studies of the cavitand revealed a development of a similar shoulder peak consistent with the oxidation-induced vase-to-kite conformation change. To support that the shoulder peak is diagnostic for a vase-to-kite conformation change, a model molecule constituting a single quinoxaline wall of the cavitand was synthesized and studied. As expected UV-Vis spectroelectrochemical studies of the cavitand arm did not display a shoulder peak below 300 nm. The oxidation-induced vase-to-kite conformation is further confirmed by the distinctive upfield shift in 1H chemical shift of the methine signal. Key words: redox active, thianthrene, resorcinarene cavitands, electrochemical switching, conformation change National Science Foundation (U.S.). Center for Energy Efficient Electronics Science (Award ECCS0939514) Singapore. Agency for Science, Technology and Research (Graduate Scholarship) 2018-04-13T18:35:34Z 2018-04-13T18:35:34Z 2016-11 2016-10 Article http://purl.org/eprint/type/JournalArticle 0039-7881 1437-210X http://hdl.handle.net/1721.1/114719 Ong, Wen, et al. “Redox Switchable Thianthrene Cavitands.” Synthesis, vol. 49, no. 02, Nov. 2016, pp. 358–64. https://orcid.org/0000-0002-2868-8682 en_US http://dx.doi.org/10.1055/s-0036-1588659 Synthesis Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Thieme Publishing Group Prof. Swager via Erja Kajosalo |
| spellingShingle | Bertani, Federico Dalcanale, Enrico Ong, Wen Jie Swager, Timothy M Redox Switchable Thianthrene Cavitands |
| title | Redox Switchable Thianthrene Cavitands |
| title_full | Redox Switchable Thianthrene Cavitands |
| title_fullStr | Redox Switchable Thianthrene Cavitands |
| title_full_unstemmed | Redox Switchable Thianthrene Cavitands |
| title_short | Redox Switchable Thianthrene Cavitands |
| title_sort | redox switchable thianthrene cavitands |
| url | http://hdl.handle.net/1721.1/114719 https://orcid.org/0000-0002-2868-8682 |
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