The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub>
Complexes [Fe(X-salEen)<sub>2</sub>]BPh<sub>4</sub>·DMF, with X = Br (<b>1</b>), Cl (<b>2</b>), and F (<b>3</b>), were crystallised from <i>N</i>,<i>N</i>′-dimethylformamide with the aim of understanding the role of...
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| Format: | Article |
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MDPI AG
2022-11-01
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| Series: | Magnetochemistry |
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| Online Access: | https://www.mdpi.com/2312-7481/8/12/162 |
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| author | Rafaela T. Marques Frederico F. Martins Deniz F. Bekiş Ana I. Vicente Liliana P. Ferreira Clara S. B. Gomes Sónia Barroso Varun Kumar Yann Garcia Nuno A. G. Bandeira Maria José Calhorda Paulo N. Martinho |
| author_facet | Rafaela T. Marques Frederico F. Martins Deniz F. Bekiş Ana I. Vicente Liliana P. Ferreira Clara S. B. Gomes Sónia Barroso Varun Kumar Yann Garcia Nuno A. G. Bandeira Maria José Calhorda Paulo N. Martinho |
| author_sort | Rafaela T. Marques |
| collection | DOAJ |
| description | Complexes [Fe(X-salEen)<sub>2</sub>]BPh<sub>4</sub>·DMF, with X = Br (<b>1</b>), Cl (<b>2</b>), and F (<b>3</b>), were crystallised from <i>N</i>,<i>N</i>′-dimethylformamide with the aim of understanding the role of a high boiling point <i>N</i>,<i>N</i>′-dimethylformamide solvate in the spin crossover phenomenon. The counter ion was chosen for only being able to participate in weak intermolecular interactions. The compounds were structurally characterised by single crystal X-ray diffraction. Complex <b>1</b> crystallised in the orthorhombic space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub>, and complexes <b>2</b> and <b>3</b> in the monoclinic space group <i>P</i>2<sub>1</sub>/<i>n</i>. Even at room temperature, low spin was the predominant form, although complex <b>2</b> exhibited the largest proportion of the high-spin species according to both the magnetisation measurements and the Mössbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes <b>1</b>–<b>3</b> and the iodide analogue <b>4</b>. While all approaches reproduced the experimental structures very well, the energy balance between the high-spin and low-spin forms was harder to reproduce, though some calculations pointed to the easier spin crossover of complex <b>2</b>, as observed. Periodic calculations with the functional PBE led to very similar ΔE<sub>HS-LS</sub> values for all complexes but showed a preference for the low-spin form. However, the single-point calculations with B3LYP* showed, for the model without solvate, that the Cl complex should undergo spin crossover more easily. The molecular calculations also reflected this fact, which was more clearly defined when the cation–anion–solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes. |
| first_indexed | 2024-03-09T16:10:26Z |
| format | Article |
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| institution | Directory Open Access Journal |
| issn | 2312-7481 |
| language | English |
| last_indexed | 2024-03-09T16:10:26Z |
| publishDate | 2022-11-01 |
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| series | Magnetochemistry |
| spelling | doaj.art-dab0f38c334d411994abbc6bb90562432023-11-24T16:18:20ZengMDPI AGMagnetochemistry2312-74812022-11-0181216210.3390/magnetochemistry8120162The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub>Rafaela T. Marques0Frederico F. Martins1Deniz F. Bekiş2Ana I. Vicente3Liliana P. Ferreira4Clara S. B. Gomes5Sónia Barroso6Varun Kumar7Yann Garcia8Nuno A. G. Bandeira9Maria José Calhorda10Paulo N. Martinho11Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalBioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalBioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalBioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalLAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, PortugalUCIBIO, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, PortugalInstitute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, BelgiumInstitute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, BelgiumBioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalBioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, PortugalComplexes [Fe(X-salEen)<sub>2</sub>]BPh<sub>4</sub>·DMF, with X = Br (<b>1</b>), Cl (<b>2</b>), and F (<b>3</b>), were crystallised from <i>N</i>,<i>N</i>′-dimethylformamide with the aim of understanding the role of a high boiling point <i>N</i>,<i>N</i>′-dimethylformamide solvate in the spin crossover phenomenon. The counter ion was chosen for only being able to participate in weak intermolecular interactions. The compounds were structurally characterised by single crystal X-ray diffraction. Complex <b>1</b> crystallised in the orthorhombic space group <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub>, and complexes <b>2</b> and <b>3</b> in the monoclinic space group <i>P</i>2<sub>1</sub>/<i>n</i>. Even at room temperature, low spin was the predominant form, although complex <b>2</b> exhibited the largest proportion of the high-spin species according to both the magnetisation measurements and the Mössbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes <b>1</b>–<b>3</b> and the iodide analogue <b>4</b>. While all approaches reproduced the experimental structures very well, the energy balance between the high-spin and low-spin forms was harder to reproduce, though some calculations pointed to the easier spin crossover of complex <b>2</b>, as observed. Periodic calculations with the functional PBE led to very similar ΔE<sub>HS-LS</sub> values for all complexes but showed a preference for the low-spin form. However, the single-point calculations with B3LYP* showed, for the model without solvate, that the Cl complex should undergo spin crossover more easily. The molecular calculations also reflected this fact, which was more clearly defined when the cation–anion–solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes.https://www.mdpi.com/2312-7481/8/12/162spin crossoverhalogenDFTFe(III) |
| spellingShingle | Rafaela T. Marques Frederico F. Martins Deniz F. Bekiş Ana I. Vicente Liliana P. Ferreira Clara S. B. Gomes Sónia Barroso Varun Kumar Yann Garcia Nuno A. G. Bandeira Maria José Calhorda Paulo N. Martinho The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> Magnetochemistry spin crossover halogen DFT Fe(III) |
| title | The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> |
| title_full | The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> |
| title_fullStr | The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> |
| title_full_unstemmed | The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> |
| title_short | The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)<sub>2</sub>]BPh<sub>4</sub> |
| title_sort | halogen effect on the magnetic behaviour of dimethylformamide solvates in fe halide saleen sub 2 sub bph sub 4 sub |
| topic | spin crossover halogen DFT Fe(III) |
| url | https://www.mdpi.com/2312-7481/8/12/162 |
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