Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors
A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the <i>meso</i> positions were prepared by using Ullmann methodology or more classical Buchwald–Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained,...
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MDPI AG
2023-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/11/4405 |
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| author | Mary-Ambre Carvalho Khalissa Merahi Julien Haumesser Ana Mafalda Vaz Martins Pereira Nathalie Parizel Jean Weiss Maylis Orio Vincent Maurel Laurent Ruhlmann Sylvie Choua Romain Ruppert |
| author_facet | Mary-Ambre Carvalho Khalissa Merahi Julien Haumesser Ana Mafalda Vaz Martins Pereira Nathalie Parizel Jean Weiss Maylis Orio Vincent Maurel Laurent Ruhlmann Sylvie Choua Romain Ruppert |
| author_sort | Mary-Ambre Carvalho |
| collection | DOAJ |
| description | A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the <i>meso</i> positions were prepared by using Ullmann methodology or more classical Buchwald–Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data. |
| first_indexed | 2024-03-11T03:01:36Z |
| format | Article |
| id | doaj.art-5f5d65ab13414bb2b67377346e2b9d6a |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T03:01:36Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-5f5d65ab13414bb2b67377346e2b9d6a2023-11-18T08:16:11ZengMDPI AGMolecules1420-30492023-05-012811440510.3390/molecules28114405Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine DonorsMary-Ambre Carvalho0Khalissa Merahi1Julien Haumesser2Ana Mafalda Vaz Martins Pereira3Nathalie Parizel4Jean Weiss5Maylis Orio6Vincent Maurel7Laurent Ruhlmann8Sylvie Choua9Romain Ruppert10Institut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceCampus of St Jérôme, Aix-Marseille University, CNRS, Centrale Marseille, iSm2, CEDEX 20, 13397 Marseille, FranceSyMMES, UMR 5819 CEA Grenoble/CNRS/Université Grenoble-Alpes, CEA Grenoble, 17 rue des Martyrs, CEDEX 9, 38054 Grenoble, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceInstitut de Chimie, UMR CNRS 7177, Université de Strasbourg, Institut Le Bel, 4 rue Blaise Pascal, 67000 Strasbourg, FranceA series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the <i>meso</i> positions were prepared by using Ullmann methodology or more classical Buchwald–Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data.https://www.mdpi.com/1420-3049/28/11/4405porphyrinoidsphenothiazineradical cationEPR spectroscopyENDORHYSCORE |
| spellingShingle | Mary-Ambre Carvalho Khalissa Merahi Julien Haumesser Ana Mafalda Vaz Martins Pereira Nathalie Parizel Jean Weiss Maylis Orio Vincent Maurel Laurent Ruhlmann Sylvie Choua Romain Ruppert Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors Molecules porphyrinoids phenothiazine radical cation EPR spectroscopy ENDOR HYSCORE |
| title | Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors |
| title_full | Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors |
| title_fullStr | Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors |
| title_full_unstemmed | Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors |
| title_short | Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors |
| title_sort | syntheses and electrochemical and epr studies of porphyrins functionalized with bulky aromatic amine donors |
| topic | porphyrinoids phenothiazine radical cation EPR spectroscopy ENDOR HYSCORE |
| url | https://www.mdpi.com/1420-3049/28/11/4405 |
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