{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,11,2]],"date-time":"2025-11-02T10:17:10Z","timestamp":1762078630093,"version":"build-2065373602"},"reference-count":41,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2022,11,22]],"date-time":"2022-11-22T00:00:00Z","timestamp":1669075200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e a Tecnologia (FCT)","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"]}]},{"name":"Fonds de la Recherche Scientifique (FNRS)","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"]}]},{"name":"Royal Society of Chemistry (RSC)","award":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"],"award-info":[{"award-number":["UIDB\/00100\/2020","UIDP\/00100\/2020","LA\/P\/0056\/2020","UIDB\/04046\/2020","UIDP\/04046\/2020","UIDB\/50006\/2020","UIDP\/50006\/2020","LA\/P\/0008\/2020","UIDB\/04378\/2020","UIDP\/04378\/2020","PTDC\/QUI-QFI\/29236\/2017","PTDCQUI-QIN0252_2021","CEECIND\/00509\/2017","PDR T.0095.21","R21-7511142525"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Magnetochemistry"],"abstract":"<jats:p>Complexes [Fe(X-salEen)2]BPh4\u00b7DMF, with X = Br (1), Cl (2), and F (3), were crystallised from N,N\u2032-dimethylformamide with the aim of understanding the role of a high boiling point N,N\u2032-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 M\u00f6ssbauer spectra. Density Functional Theory calculations were performed both on the periodic solids and on molecular models for complexes 1\u20133 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 \u0394EHS-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\u2013anion\u2013solvate model was used. In the other models there was not much difference between the Cl, Br, and I complexes.<\/jats:p>","DOI":"10.3390\/magnetochemistry8120162","type":"journal-article","created":{"date-parts":[[2022,11,22]],"date-time":"2022-11-22T03:08:37Z","timestamp":1669086517000},"page":"162","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4"],"prefix":"10.3390","volume":"8","author":[{"given":"Rafaela T.","family":"Marques","sequence":"first","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1458-2526","authenticated-orcid":false,"given":"Frederico F.","family":"Martins","sequence":"additional","affiliation":[{"name":"BioISI\u2014Biosystems & Integrative Sciences Institute, Departamento de Qu\u00edmica e Bioqu\u00edmia, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4535-6505","authenticated-orcid":false,"given":"Deniz F.","family":"Beki\u015f","sequence":"additional","affiliation":[{"name":"BioISI\u2014Biosystems & Integrative Sciences Institute, Departamento de Qu\u00edmica e Bioqu\u00edmia, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"given":"Ana I.","family":"Vicente","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"given":"Liliana P.","family":"Ferreira","sequence":"additional","affiliation":[{"name":"BioISI\u2014Biosystems & Integrative Sciences Institute, Departamento de Qu\u00edmica e Bioqu\u00edmia, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"},{"name":"Department of Physics, University of Coimbra, 3004-516 Coimbra, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3672-0045","authenticated-orcid":false,"given":"Clara S. B.","family":"Gomes","sequence":"additional","affiliation":[{"name":"LAQV-REQUIMTE, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"},{"name":"UCIBIO, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"},{"name":"i4HB, Faculdade de Ci\u00eancias e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6152-265X","authenticated-orcid":false,"given":"S\u00f3nia","family":"Barroso","sequence":"additional","affiliation":[{"name":"UCIBIO, Departamento de Qu\u00edmica, Faculdade de Ci\u00eancias e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"},{"name":"i4HB, Faculdade de Ci\u00eancias e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal"}]},{"given":"Varun","family":"Kumar","sequence":"additional","affiliation":[{"name":"Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN\/MOST), Universit\u00e9 Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3105-0735","authenticated-orcid":false,"given":"Yann","family":"Garcia","sequence":"additional","affiliation":[{"name":"Institute of Condensed Matter and Nanosciences, Molecular Chemistry, Materials and Catalysis (IMCN\/MOST), Universit\u00e9 Catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5754-7328","authenticated-orcid":false,"given":"Nuno A. G.","family":"Bandeira","sequence":"additional","affiliation":[{"name":"BioISI\u2014Biosystems & Integrative Sciences Institute, Departamento de Qu\u00edmica e Bioqu\u00edmia, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"given":"Maria Jos\u00e9","family":"Calhorda","sequence":"additional","affiliation":[{"name":"BioISI\u2014Biosystems & Integrative Sciences Institute, Departamento de Qu\u00edmica e Bioqu\u00edmia, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2552-6263","authenticated-orcid":false,"given":"Paulo N.","family":"Martinho","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,11,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Halcrow, M.A. (2013). 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