The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4
(2022) Magnetochemistry — Vol. 8, n° 12, p. 162 (2022)
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Martins, Frederico F. 
Bekiş, Deniz F.
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- first_pagesettingsOrder Article Reprints Open AccessArticle The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 by Rafaela T. Marques 1,Frederico F. Martins 2,†ORCID,Deniz F. Bekiş 2,‡ORCID,Ana I. Vicente 1,Liliana P. Ferreira 2,3,Clara S. B. Gomes 4,5,6ORCID,Sónia Barroso 5,6,§ORCID,Varun Kumar 7,Yann Garcia 7ORCID,Nuno A. G. Bandeira 2ORCID,Maria José Calhorda 2 andPaulo N. Martinho 1,*ORCID 1 Centro de Química Estrutural, Institute of Molecular Sciences, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal 2 BioISI—Biosystems & Integrative Sciences Institute, Departamento de Química e Bioquímia, Faculdade de Ciências, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal 3 Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal 4 LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 5 UCIBIO, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 6 i4HB, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal 7 Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN/MOST), Université Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium * Author to whom correspondence should be addressed. † Current address: IQCC & Department Química, Universitat de Girona, Campus Montilivi (Ciències), 17003 Girona, Spain. ‡ Current address: Anorganische Chemie, Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032 Marburg, Germany. § Current address: MARE—Marine and Environmental Sciences Centre/ARNET—Aquatic Research Network, Polytechnic of Leiria, Cetemares, 2520-620 Peniche, Portugal. Magnetochemistry 2022, 8(12), 162; https://doi.org/10.3390/magnetochemistry8120162 Received: 31 October 2022 / Revised: 15 November 2022 / Accepted: 16 November 2022 / Published: 22 November 2022 (This article belongs to the Special Issue Molecular Spin Crossover Materials: Recent Trends, Emerging Properties and Applications) Download Browse Figures Review Reports Versions Notes Abstract Complexes [Fe(X-salEen)2]BPh4·DMF, with X = Br (1), Cl (2), and F (3), were crystallised from N,N′-dimethylformamide with the aim of understanding the role of a high boiling point N,N′-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 1 crystallised in the orthorhombic space group P212121, and complexes 2 and 3 in the monoclinic space group P21/n. Even at room temperature, low spin was the predominant form, although complex 2 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 1–3 and the iodide analogue 4. 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 2, as observed. Periodic calculations with the functional PBE led to very similar ΔEHS-LS 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.
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Marques, R. T., Martins, F. F., Bekiş, D. F., Vicente, A. I., Ferreira, L. P., Gomes, C. S. B., Barroso, S., Kumar, V., Garcia, Y., Bandeira, N. A. G., Calhorda, M. J., & Garcia, Y. (2022). The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4. Magnetochemistry, 8(12), 162. https://doi.org/10.3390/magnetochemistry8120162 (Original work published 2022)