The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4
| Autor(a) principal: | |
|---|---|
| Data de Publicação: | 2022 |
| Outros Autores: | , , , , , , , , , , |
| Tipo de documento: | Artigo |
| Idioma: | eng |
| Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
| Texto Completo: | http://hdl.handle.net/10362/146401 |
Resumo: | 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). |
| id |
RCAP_67aa6b8b02ea08309e3655fc872c897d |
|---|---|
| oai_identifier_str |
oai:run.unl.pt:10362/146401 |
| network_acronym_str |
RCAP |
| network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
| repository_id_str |
7160 |
| spelling |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4spin crossoverFe(III)halogenDFTFunding 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).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.LAQV@REQUIMTEUCIBIO - Applied Molecular Biosciences UnitDQ - Departamento de QuímicaRUNMarques, Rafaela T.Martins, Frederico F.Bekiş, Deniz F.Vicente, Ana I.Ferreira, Liliana P.Gomes, Clara S. B.Barroso, SóniaKumar, VarunGarcia, YannBandeira, Nuno A. G.Calhorda, Maria JoséMartinho, Paulo N.2022-12-19T22:13:08Z2022-11-222022-11-22T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article16application/pdfhttp://hdl.handle.net/10362/146401eng2312-7481PURE: 47894279https://doi.org/10.3390/magnetochemistry8120162info:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-03-11T05:27:28Zoai:run.unl.pt:10362/146401Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T03:52:36.682129Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
| dc.title.none.fl_str_mv |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| title |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| spellingShingle |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 Marques, Rafaela T. spin crossover Fe(III) halogen DFT |
| title_short |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| title_full |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| title_fullStr |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| title_full_unstemmed |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| title_sort |
The Halogen Effect on the Magnetic Behaviour of Dimethylformamide Solvates in [Fe(halide-salEen)2]BPh4 |
| author |
Marques, Rafaela T. |
| author_facet |
Marques, Rafaela T. Martins, Frederico F. Bekiş, Deniz F. Vicente, Ana I. Ferreira, Liliana P. Gomes, Clara S. B. Barroso, Sónia Kumar, Varun Garcia, Yann Bandeira, Nuno A. G. Calhorda, Maria José Martinho, Paulo N. |
| author_role |
author |
| author2 |
Martins, Frederico F. Bekiş, Deniz F. Vicente, Ana I. Ferreira, Liliana P. Gomes, Clara S. B. Barroso, Sónia Kumar, Varun Garcia, Yann Bandeira, Nuno A. G. Calhorda, Maria José Martinho, Paulo N. |
| author2_role |
author author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
LAQV@REQUIMTE UCIBIO - Applied Molecular Biosciences Unit DQ - Departamento de Química RUN |
| dc.contributor.author.fl_str_mv |
Marques, Rafaela T. Martins, Frederico F. Bekiş, Deniz F. Vicente, Ana I. Ferreira, Liliana P. Gomes, Clara S. B. Barroso, Sónia Kumar, Varun Garcia, Yann Bandeira, Nuno A. G. Calhorda, Maria José Martinho, Paulo N. |
| dc.subject.por.fl_str_mv |
spin crossover Fe(III) halogen DFT |
| topic |
spin crossover Fe(III) halogen DFT |
| description |
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). |
| publishDate |
2022 |
| dc.date.none.fl_str_mv |
2022-12-19T22:13:08Z 2022-11-22 2022-11-22T00:00:00Z |
| dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
| dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| status_str |
publishedVersion |
| dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10362/146401 |
| url |
http://hdl.handle.net/10362/146401 |
| dc.language.iso.fl_str_mv |
eng |
| language |
eng |
| dc.relation.none.fl_str_mv |
2312-7481 PURE: 47894279 https://doi.org/10.3390/magnetochemistry8120162 |
| dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
| eu_rights_str_mv |
openAccess |
| dc.format.none.fl_str_mv |
16 application/pdf |
| dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
| instname_str |
Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
| instacron_str |
RCAAP |
| institution |
RCAAP |
| reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
| collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
| repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
| repository.mail.fl_str_mv |
|
| _version_ |
1799138117518622720 |