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The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4

2022-11-22Artigo científico Acesso aberto
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dc.contributor.authorMarques, Rafaela T.
dc.contributor.authorMartins, Frederico F.
dc.contributor.authorBekiş, Deniz F.
dc.contributor.authorVicente, Ana I.
dc.contributor.authorFerreira, Liliana P.
dc.contributor.authorGomes, Clara S. B.
dc.contributor.authorBarroso, Sónia
dc.contributor.authorKumar, Varun
dc.contributor.authorGarcia, Yann
dc.contributor.authorBandeira, Nuno A. G.
dc.contributor.authorCalhorda, Maria José
dc.contributor.authorMartinho, Paulo N.
dc.contributor.institutionLAQV@REQUIMTE
dc.contributor.institutionUCIBIO - Applied Molecular Biosciences Unit
dc.contributor.institutionDQ - Departamento de Química
dc.contributor.pblMDPI - Multidisciplinary Digital Publishing Institute
dc.date.accessioned2022-12-19T22:13:08Z
dc.date.available2022-12-19T22:13:08Z
dc.date.issued2022-11-22
dc.descriptionFunding Research was funded by Fundação para a Ciência e a Tecnologia (FCT): projects LA/P/0056/2020, LA/P/0140/2020; Fonds de la Recherche Scientifique (FNRS): PDR T.0095.21); Portugal2020: CENTRO-01-0145-FEDER-000018; Royal Society of Chemistry (RSC): R21-7511142525. Acknowledgments Centro de Química Estrutural (CQE) and Institute of Molecular Sciences (IMS) acknowledge the financial support of Fundação para a Ciência e a Tecnologia (FCT): Projects LA/P/0056/2020, respectively. This work was supported by the FNRS (PDR T.0095.21). Clara S. B. Gomes acknowledges the Associate Laboratory for Green Chemistry—LAQV, the Applied Molecular Biosciences Unit—UCIBIO and Associated Laboratory i4HB, which are financed by national funds from FCT (LA/P/0140/2020, respectively). Sónia Barroso thanks project SmartBioR for financial support (CENTRO-01-0145-FEDER-000018) and Centro de Química Estrutural for the access to crystallography facilities. Paulo N. Martinho thanks FCT and RSC for financial support (grants PTDCQUI-QIN0252_2021 and R21-7511142525).
dc.description.abstractComplexes [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.en
dc.description.versionpublishersversion
dc.description.versionpublished
dc.format.extent16
dc.format.extent1217209
dc.identifier.doi10.3390/magnetochemistry8120162
dc.identifier.issn2312-7481
dc.identifier.otherPURE: 47894279
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dc.identifier.otherScopus: 85144709732
dc.identifier.urihttp://hdl.handle.net/10362/146401
dc.identifier.urlhttps://doi.org/10.3390/magnetochemistry8120162
dc.language.isoeng
dc.peerreviewedyes
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dc.relationCentro de Química Estrutural
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dc.relationBiosystems and Integrative Sciences Institute
dc.relationAssociated Laboratory for Green Chemistry - Clean Technologies and Processes
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dc.relationCentro de Química Estrutural
dc.relationBiosystems and Integrative Sciences Institute
dc.relationinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F00100%2F2020/PT
dc.relationinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04046%2F2020/PT
dc.relationAssociated Laboratory for Green Chemistry - Clean Technologies and Processes
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dc.relationApplied Molecular Biosciences Unit
dc.relationApplied Molecular Biosciences Unit
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dc.relationNot Available
dc.relationinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04378%2F2020/PT
dc.relationinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04378%2F2020/PT
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dc.subjectspin crossover
dc.subjectFe(III)
dc.subjecthalogen
dc.subjectDFT
dc.titleThe Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4en
dc.typejournal article
degois.publication.issue12
degois.publication.titleMagnetochemistry
degois.publication.volume8
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