TY - JOUR
T1 - The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4
AU - Marques, Rafaela T.
AU - Martins, Frederico F.
AU - Bekiş, Deniz F.
AU - Vicente, Ana I.
AU - Ferreira, Liliana P.
AU - Gomes, Clara S. B.
AU - Barroso, Sónia
AU - Kumar, Varun
AU - Garcia, Yann
AU - Bandeira, Nuno A. G.
AU - Calhorda, Maria José
AU - Martinho, Paulo N.
N1 - info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0008%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FQUI-QFI%2F29236%2F2017/PT#
info:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FQUI-QFI%2F29236%2F2017/PT#
info:eu-repo/grantAgreement/FCT/CEEC IND 2017/CEECIND%2F00509%2F2017%2FCP1387%2FCT0029/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F00100%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04046%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F50006%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/LA%2FP%2F0008%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDB%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UIDP%2F04378%2F2020/PT#
info:eu-repo/grantAgreement/FCT/3599-PPCDT/PTDC%2FQUI-QFI%2F29236%2F2017/PT#
info:eu-repo/grantAgreement/FCT/CEEC IND 2017/CEECIND%2F00509%2F2017%2FCP1387%2FCT0029/PT#
Funding
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).
PY - 2022/11/22
Y1 - 2022/11/22
N2 - 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.
AB - 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.
KW - spin crossover
KW - Fe(III)
KW - halogen
KW - DFT
UR - https://doi.org/10.3390/magnetochemistry8120162
U2 - 10.3390/magnetochemistry8120162
DO - 10.3390/magnetochemistry8120162
M3 - Article
SN - 2312-7481
VL - 8
JO - Magnetochemistry
JF - Magnetochemistry
IS - 12
M1 - 162
ER -