Trifluoromethyl-substituted tetrathiafulvalenes
A series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated fro...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2015-05-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.11.73 |
| _version_ | 1818671703288446976 |
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| author | Olivier Jeannin Frédéric Barrière Marc Fourmigué |
| author_facet | Olivier Jeannin Frédéric Barrière Marc Fourmigué |
| author_sort | Olivier Jeannin |
| collection | DOAJ |
| description | A series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations. Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the σmeta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that the deformation of the unsymmetrically substituted dithiole rings, when bearing one, or two different EWG, and attributed to the mesomeric effect of ester or nitrile groups, is not notably modified or counter-balanced by the introduction of a neighboring trifluoromethyl group. DFT calculations confirm these observations and also show that the low energy HOMO–LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO→LUMO + 1 transition. Despite relatively high oxidation potentials, these donor molecules with CF3 EWG can be involved in charge transfer complexes or cation radical salts, as reported here for the CF3-subsituted EDT-TTF donor molecule. A neutral charge transfer complex with TCNQ, (EDT-TTF-CF3)2(TCNQ) was isolated and characterized through alternated stacks of EDT-TTF-CF3 dimers and TCNQ in the solid state. A radical cation salt of EDT-TTF-CF3 is also obtained upon electrocrystallisation in the presence of the FeCl4− anion. In this salt, formulated as (EDT-TTF-CF3)(FeCl4), the (EDT-TTF-CF3)+• radical cations are associated two-by-two into centrosymmetric dyads with a strong pairing of the radical species in a singlet state. |
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| id | doaj.art-f2c5aedd4a214f808dfa83560f2cc979 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-17T07:28:13Z |
| publishDate | 2015-05-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-f2c5aedd4a214f808dfa83560f2cc9792022-12-21T21:58:34ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972015-05-0111164765810.3762/bjoc.11.731860-5397-11-73Trifluoromethyl-substituted tetrathiafulvalenesOlivier Jeannin0Frédéric Barrière1Marc Fourmigué2Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes I, Campus de Beaulieu, 35042 Rennes, FranceInstitut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes I, Campus de Beaulieu, 35042 Rennes, FranceInstitut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes I, Campus de Beaulieu, 35042 Rennes, FranceA series of tetrathiafulvalenes functionalized with one or two trifluoromethyl electron-withdrawing groups (EWG) is obtained by phosphite coupling involving CF3-substituted 1,3-dithiole-2-one derivatives. The relative effects of the EWG such as CF3, CO2Me and CN on the TTF core were investigated from a combination of structural, electrochemical, spectrochemical and theoretical investigations. Electrochemical data confirm the good correlations between the first oxidation potential of the TTF derivatives and the σmeta Hammet parameter, thus in the order CO2Me < CF3 < CN, indicating that, in any case, the mesomeric effect of the substituents is limited. Besides, crystal structure determinations show that the deformation of the unsymmetrically substituted dithiole rings, when bearing one, or two different EWG, and attributed to the mesomeric effect of ester or nitrile groups, is not notably modified or counter-balanced by the introduction of a neighboring trifluoromethyl group. DFT calculations confirm these observations and also show that the low energy HOMO–LUMO absorption band found in nitrile or ester-substituted TTFs is not found in TTF-CF3, where, as in TTF itself, the low energy absorption band is essentially attributable to a HOMO→LUMO + 1 transition. Despite relatively high oxidation potentials, these donor molecules with CF3 EWG can be involved in charge transfer complexes or cation radical salts, as reported here for the CF3-subsituted EDT-TTF donor molecule. A neutral charge transfer complex with TCNQ, (EDT-TTF-CF3)2(TCNQ) was isolated and characterized through alternated stacks of EDT-TTF-CF3 dimers and TCNQ in the solid state. A radical cation salt of EDT-TTF-CF3 is also obtained upon electrocrystallisation in the presence of the FeCl4− anion. In this salt, formulated as (EDT-TTF-CF3)(FeCl4), the (EDT-TTF-CF3)+• radical cations are associated two-by-two into centrosymmetric dyads with a strong pairing of the radical species in a singlet state.https://doi.org/10.3762/bjoc.11.73electrochemistryelectron withdrawing group (EWG)fluorinetetrathiafulvalene (TTF) |
| spellingShingle | Olivier Jeannin Frédéric Barrière Marc Fourmigué Trifluoromethyl-substituted tetrathiafulvalenes Beilstein Journal of Organic Chemistry electrochemistry electron withdrawing group (EWG) fluorine tetrathiafulvalene (TTF) |
| title | Trifluoromethyl-substituted tetrathiafulvalenes |
| title_full | Trifluoromethyl-substituted tetrathiafulvalenes |
| title_fullStr | Trifluoromethyl-substituted tetrathiafulvalenes |
| title_full_unstemmed | Trifluoromethyl-substituted tetrathiafulvalenes |
| title_short | Trifluoromethyl-substituted tetrathiafulvalenes |
| title_sort | trifluoromethyl substituted tetrathiafulvalenes |
| topic | electrochemistry electron withdrawing group (EWG) fluorine tetrathiafulvalene (TTF) |
| url | https://doi.org/10.3762/bjoc.11.73 |
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