Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges
We define, experimentally, the effect of intramolecular electric fields, generated from the positive charge of ferricenium cations, over the oxidation potential of 2,2,6,6-tetramethyl-1-piperdinyloxy (TEMPO). We synthesized a TEMPO derivative, where the nitroxide is linked to a ferrocene unit. We ha...
| Main Authors: | , , |
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| Format: | Journal Article |
| Language: | English |
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WILEY-V C H VERLAG GMBH
2020
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| Online Access: | http://purl.org/au-research/grants/arc/CE140100036 http://hdl.handle.net/20.500.11937/91722 |
| _version_ | 1848765578794237952 |
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| author | Zhang, L. Ciampi, Simone Gooding, J.J. |
| author_facet | Zhang, L. Ciampi, Simone Gooding, J.J. |
| author_sort | Zhang, L. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | We define, experimentally, the effect of intramolecular electric fields, generated from the positive charge of ferricenium cations, over the oxidation potential of 2,2,6,6-tetramethyl-1-piperdinyloxy (TEMPO). We synthesized a TEMPO derivative, where the nitroxide is linked to a ferrocene unit. We have used this molecule to study the influence on the electrostatic cross-talk between positively charged ferriceniums and TEMPO units by solvent dielectric, level of electrolytic support, and Lewis acid/base character of electrolyte ions. The magnitude of thermodynamic anodic shift of the TEMPO oxidation, after the ferrocene unit is converted to a ferricenium cation, increases with decreasing dielectric constant of the solvent, electrolytic concentration, and Lewis basicity strength (i. e. between ferriceniums and electrolyte anions). This work demonstrates an approach to use electrostatic forces, here delivered by intramolecular charged cations, to tune the oxidation energy for nitroxides in ionic solutions. |
| first_indexed | 2025-11-14T11:37:29Z |
| format | Journal Article |
| id | curtin-20.500.11937-91722 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-14T11:37:29Z |
| publishDate | 2020 |
| publisher | WILEY-V C H VERLAG GMBH |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-917222023-05-30T09:15:03Z Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges Zhang, L. Ciampi, Simone Gooding, J.J. Science & Technology Physical Sciences Electrochemistry nitroxide potential separation ferricenium charges electrostatic regulation electrical double layer ORIENTED ELECTRIC-FIELDS CATALYSIS SELECTIVITY MONOLAYERS We define, experimentally, the effect of intramolecular electric fields, generated from the positive charge of ferricenium cations, over the oxidation potential of 2,2,6,6-tetramethyl-1-piperdinyloxy (TEMPO). We synthesized a TEMPO derivative, where the nitroxide is linked to a ferrocene unit. We have used this molecule to study the influence on the electrostatic cross-talk between positively charged ferriceniums and TEMPO units by solvent dielectric, level of electrolytic support, and Lewis acid/base character of electrolyte ions. The magnitude of thermodynamic anodic shift of the TEMPO oxidation, after the ferrocene unit is converted to a ferricenium cation, increases with decreasing dielectric constant of the solvent, electrolytic concentration, and Lewis basicity strength (i. e. between ferriceniums and electrolyte anions). This work demonstrates an approach to use electrostatic forces, here delivered by intramolecular charged cations, to tune the oxidation energy for nitroxides in ionic solutions. 2020 Journal Article http://hdl.handle.net/20.500.11937/91722 10.1002/celc.202000817 English http://purl.org/au-research/grants/arc/CE140100036 http://purl.org/au-research/grants/arc/FL150100060 http://purl.org/au-research/grants/arc/DP190102659 http://purl.org/au-research/grants/arc/FT190100148 WILEY-V C H VERLAG GMBH fulltext |
| spellingShingle | Science & Technology Physical Sciences Electrochemistry nitroxide potential separation ferricenium charges electrostatic regulation electrical double layer ORIENTED ELECTRIC-FIELDS CATALYSIS SELECTIVITY MONOLAYERS Zhang, L. Ciampi, Simone Gooding, J.J. Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title | Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title_full | Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title_fullStr | Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title_full_unstemmed | Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title_short | Electrostatic Regulation of TEMPO Oxidation by Distal Molecular Charges |
| title_sort | electrostatic regulation of tempo oxidation by distal molecular charges |
| topic | Science & Technology Physical Sciences Electrochemistry nitroxide potential separation ferricenium charges electrostatic regulation electrical double layer ORIENTED ELECTRIC-FIELDS CATALYSIS SELECTIVITY MONOLAYERS |
| url | http://purl.org/au-research/grants/arc/CE140100036 http://purl.org/au-research/grants/arc/CE140100036 http://purl.org/au-research/grants/arc/CE140100036 http://purl.org/au-research/grants/arc/CE140100036 http://hdl.handle.net/20.500.11937/91722 |