Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes
Reaction of Fe(II) with the tris-(pyridin-2-yl)ethoxymethane (py<sub>3</sub>C-OEt) tripodal ligand in the presence of the pseudohalide ancillary NCSe<sup>−</sup> (E = S, Se, BH<sub>3</sub>) ligand leads to the mononuclear complex [Fe(py<sub>3</sub>C-OE...
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MDPI AG
2021-05-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/7/6/75 |
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| author | Emmelyne Cuza Samia Benmansour Nathalie Cosquer Françoise Conan Carlos J. Gómez-García Smail Triki |
| author_facet | Emmelyne Cuza Samia Benmansour Nathalie Cosquer Françoise Conan Carlos J. Gómez-García Smail Triki |
| author_sort | Emmelyne Cuza |
| collection | DOAJ |
| description | Reaction of Fe(II) with the tris-(pyridin-2-yl)ethoxymethane (py<sub>3</sub>C-OEt) tripodal ligand in the presence of the pseudohalide ancillary NCSe<sup>−</sup> (E = S, Se, BH<sub>3</sub>) ligand leads to the mononuclear complex [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>][Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sub>2</sub>·2CH<sub>3</sub>CN (<b>3</b>), which has been characterised as an isomorph of the two previously reported complexes, Fe(py<sub>3</sub>C-OEt)<sub>2</sub>][Fe(py<sub>3</sub>C-OEt)(NCE)<sub>3</sub>]<sub>2</sub>·2CH<sub>3</sub>CN, with E = S (<b>1</b>), BH<sub>3</sub> (<b>2</b>). X-ray powder diffraction of the three complexes (<b>1</b>–<b>3</b>), associated with the previously reported single crystal structures of <b>1</b>–<b>2</b>, revealed a monomeric isomorph structure for <b>3</b>, formed by the spin crossover (<i>SCO</i>) anionic [Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sup>−</sup> complex, associated with the low spin (<i>LS</i>) [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>]<sup>2+</sup> cationic complex and two solvent acetonitrile molecules. In the [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>]<sup>2+</sup> complex, the metal ion environment involves two py<sub>3</sub>C-OEt tridentate ligands, while the [Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sup>−</sup> anion displays a hexacoordinated environment involving three N-donor atoms of one py<sub>3</sub>C-OEt ligand and three nitrogen atoms arising from the three (NCSe)<sup>−</sup> coligands. The magnetic studies for <b>3</b> performed in the temperature range 300-5-400 K, indicated the presence of a two-step SCO transition centred around 170 and 298 K, while when the sample was heated at 400 K until its complete desolvation, the magnetic behaviour of the high temperature transition (<i>T</i><sub>1/2</sub> = 298 K) shifted to a lower temperature until the two-step behaviour merged with a gradual one-step transition at ca. 216 K. |
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| spelling | doaj.art-b30103ca6bfc4ea08300e35a901742a52023-11-21T21:02:09ZengMDPI AGMagnetochemistry2312-74812021-05-01767510.3390/magnetochemistry7060075Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph ComplexesEmmelyne Cuza0Samia Benmansour1Nathalie Cosquer2Françoise Conan3Carlos J. Gómez-García4Smail Triki5Univ Brest, CNRS, CEMCA, 6 Avenue Le Gorgeu, C.S. 93837, CEDEX 3, 29238 Brest, FranceInstituto de Ciencia Molecular (ICMol), Departamento de Química Inorgánica, Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, SpainUniv Brest, CNRS, CEMCA, 6 Avenue Le Gorgeu, C.S. 93837, CEDEX 3, 29238 Brest, FranceUniv Brest, CNRS, CEMCA, 6 Avenue Le Gorgeu, C.S. 93837, CEDEX 3, 29238 Brest, FranceInstituto de Ciencia Molecular (ICMol), Departamento de Química Inorgánica, Universidad de Valencia, C/Catedrático José Beltrán 2, 46980 Paterna, SpainUniv Brest, CNRS, CEMCA, 6 Avenue Le Gorgeu, C.S. 93837, CEDEX 3, 29238 Brest, FranceReaction of Fe(II) with the tris-(pyridin-2-yl)ethoxymethane (py<sub>3</sub>C-OEt) tripodal ligand in the presence of the pseudohalide ancillary NCSe<sup>−</sup> (E = S, Se, BH<sub>3</sub>) ligand leads to the mononuclear complex [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>][Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sub>2</sub>·2CH<sub>3</sub>CN (<b>3</b>), which has been characterised as an isomorph of the two previously reported complexes, Fe(py<sub>3</sub>C-OEt)<sub>2</sub>][Fe(py<sub>3</sub>C-OEt)(NCE)<sub>3</sub>]<sub>2</sub>·2CH<sub>3</sub>CN, with E = S (<b>1</b>), BH<sub>3</sub> (<b>2</b>). X-ray powder diffraction of the three complexes (<b>1</b>–<b>3</b>), associated with the previously reported single crystal structures of <b>1</b>–<b>2</b>, revealed a monomeric isomorph structure for <b>3</b>, formed by the spin crossover (<i>SCO</i>) anionic [Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sup>−</sup> complex, associated with the low spin (<i>LS</i>) [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>]<sup>2+</sup> cationic complex and two solvent acetonitrile molecules. In the [Fe(py<sub>3</sub>C-OEt)<sub>2</sub>]<sup>2+</sup> complex, the metal ion environment involves two py<sub>3</sub>C-OEt tridentate ligands, while the [Fe(py<sub>3</sub>C-OEt)(NCSe)<sub>3</sub>]<sup>−</sup> anion displays a hexacoordinated environment involving three N-donor atoms of one py<sub>3</sub>C-OEt ligand and three nitrogen atoms arising from the three (NCSe)<sup>−</sup> coligands. The magnetic studies for <b>3</b> performed in the temperature range 300-5-400 K, indicated the presence of a two-step SCO transition centred around 170 and 298 K, while when the sample was heated at 400 K until its complete desolvation, the magnetic behaviour of the high temperature transition (<i>T</i><sub>1/2</sub> = 298 K) shifted to a lower temperature until the two-step behaviour merged with a gradual one-step transition at ca. 216 K.https://www.mdpi.com/2312-7481/7/6/75tripodal ligandspseudohalide coligandsiron complexspin crossovermagnetic properties |
| spellingShingle | Emmelyne Cuza Samia Benmansour Nathalie Cosquer Françoise Conan Carlos J. Gómez-García Smail Triki Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes Magnetochemistry tripodal ligands pseudohalide coligands iron complex spin crossover magnetic properties |
| title | Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes |
| title_full | Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes |
| title_fullStr | Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes |
| title_full_unstemmed | Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes |
| title_short | Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes |
| title_sort | solvent induced hysteresis loop in anionic spin crossover sco isomorph complexes |
| topic | tripodal ligands pseudohalide coligands iron complex spin crossover magnetic properties |
| url | https://www.mdpi.com/2312-7481/7/6/75 |
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