Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests
Glycoluril-based molecular clips incorporating tetrathiafulvalene (TTF) sidewalls have been synthesized through different strategies with the aim of investigating the effect of electrochemical and spatial properties for binding neutral accepting guests. We have in particular focused our study on the...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-06-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.11.115 |
| _version_ | 1818556117397012480 |
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| author | Yoann Cotelle Marie Hardouin-Lerouge Stéphanie Legoupy Olivier Alévêque Eric Levillain Piétrick Hudhomme |
| author_facet | Yoann Cotelle Marie Hardouin-Lerouge Stéphanie Legoupy Olivier Alévêque Eric Levillain Piétrick Hudhomme |
| author_sort | Yoann Cotelle |
| collection | DOAJ |
| description | Glycoluril-based molecular clips incorporating tetrathiafulvalene (TTF) sidewalls have been synthesized through different strategies with the aim of investigating the effect of electrochemical and spatial properties for binding neutral accepting guests. We have in particular focused our study on the spacer extension in order to tune the intramolecular TTF···TTF distance within the clip and, consequently, the redox behavior of the receptor. Carried out at different concentrations in solution, electrochemical and spectroelectrochemical experiments provide evidence of mixed-valence and/or π-dimer intermolecular interactions between TTF units from two closed clips. The stepwise oxidation of each molecular clip involves an electrochemical mechanism with three one-electron processes and two charge-coupled chemical reactions, a scheme which is supported by electrochemical simulations. The fine-tunable π-donating ability of the TTF units and the cavity size allow to control binding interaction towards a strong electron acceptor such as tetrafluorotetracyanoquinodimethane (F4-TCNQ) or a weaker electron acceptor such as 1,3-dinitrobenzene (m-DNB). |
| first_indexed | 2024-12-13T23:43:19Z |
| format | Article |
| id | doaj.art-fd5d1b5aa27048218a044aafa68b0ed8 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-13T23:43:19Z |
| publishDate | 2015-06-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-fd5d1b5aa27048218a044aafa68b0ed82022-12-21T23:27:06ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-06-011111023103610.3762/bjoc.11.1151860-5397-11-115Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guestsYoann Cotelle0Marie Hardouin-Lerouge1Stéphanie Legoupy2Olivier Alévêque3Eric Levillain4Piétrick Hudhomme5Université d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceUniversité d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceUniversité d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceUniversité d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceUniversité d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceUniversité d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, FranceGlycoluril-based molecular clips incorporating tetrathiafulvalene (TTF) sidewalls have been synthesized through different strategies with the aim of investigating the effect of electrochemical and spatial properties for binding neutral accepting guests. We have in particular focused our study on the spacer extension in order to tune the intramolecular TTF···TTF distance within the clip and, consequently, the redox behavior of the receptor. Carried out at different concentrations in solution, electrochemical and spectroelectrochemical experiments provide evidence of mixed-valence and/or π-dimer intermolecular interactions between TTF units from two closed clips. The stepwise oxidation of each molecular clip involves an electrochemical mechanism with three one-electron processes and two charge-coupled chemical reactions, a scheme which is supported by electrochemical simulations. The fine-tunable π-donating ability of the TTF units and the cavity size allow to control binding interaction towards a strong electron acceptor such as tetrafluorotetracyanoquinodimethane (F4-TCNQ) or a weaker electron acceptor such as 1,3-dinitrobenzene (m-DNB).https://doi.org/10.3762/bjoc.11.115donor–acceptor interactionsglycolurilmolecular clipssupramolecular chemistrytetrathiafulvalene |
| spellingShingle | Yoann Cotelle Marie Hardouin-Lerouge Stéphanie Legoupy Olivier Alévêque Eric Levillain Piétrick Hudhomme Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests Beilstein Journal of Organic Chemistry donor–acceptor interactions glycoluril molecular clips supramolecular chemistry tetrathiafulvalene |
| title | Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests |
| title_full | Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests |
| title_fullStr | Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests |
| title_full_unstemmed | Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests |
| title_short | Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests |
| title_sort | glycoluril tetrathiafulvalene molecular clips on the influence of electronic and spatial properties for binding neutral accepting guests |
| topic | donor–acceptor interactions glycoluril molecular clips supramolecular chemistry tetrathiafulvalene |
| url | https://doi.org/10.3762/bjoc.11.115 |
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