From field-induced to zero-field SMMs associated with open/closed structures of bis(ZnDy) tetranuclear complexes: a combined magnetic, theoretical and optical study

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dc.contributor.authorZabala-Lekuona, Andoni
dc.contributor.authorLópez de Pariza, Xabier
dc.contributor.authorDíaz-Ortega, Ismael F.
dc.contributor.authorCepeda, Javier
dc.contributor.authorNojiri, Hiroyuki
dc.contributor.authorGritsan, Nina P.
dc.contributor.authorDmitriev, Alexey A.
dc.contributor.authorLópez Ortega, Alberto
dc.contributor.authorRodríguez-Diéguez, Antonio
dc.contributor.authorSeco, José M.
dc.contributor.authorColacio, Enrique
dc.contributor.departmentCienciases_ES
dc.contributor.departmentZientziakeu
dc.contributor.departmentInstitute for Advanced Materials and Mathematics - INAMAT2en
dc.contributor.funderUniversidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA2020es
dc.date.accessioned2024-08-08T15:11:20Z
dc.date.available2024-08-08T15:11:20Z
dc.date.issued2024
dc.date.updated2024-08-08T14:42:24Z
dc.description.abstractWe have prepared a bis(compartmental) Mannich base ligand H4L (1,4,8,11-tetraaza-1,4,8,11-tetrakis(2-hydroxy-3-methoxy-5-methylbenzyl)cyclotetradecane) specifically designed to obtain bis(TMIILnIII) tetranuclear complexes (TM = transition metal). In this regard, we have succeeded in obtaining three new complexes of the formula [Zn2(μ-L)(μ-OAc)Dy2(NO3)2]·[Zn2(μ-L)(μ-OAc)Dy2(NO3)(OAc)]·4CHCl3·2MeOH (1) and [TM2(μ-H2L)2(μ-succinate)Ln2(NO3)2] (NO3)2·2H2O·6MeOH (TMII = Zn, LnIII = Dy (2); TMII = Co, LnIII = Dy (3)). Compound 1 contains two different bis(ZnDy) tetranuclear molecules that cocrystallize in the structure, in which acetato bridging ligands connect the ZnII and DyIII ions within each ZnDy subunit. This compound does not exhibit slow magnetic relaxation at zero field, but it is activated in the presence of an applied dc magnetic field and/or by Dy/Y magnetic dilution, showing two relaxation processes corresponding to each of the two different bis(ZnDy) units found in the structure. As revealed by the theoretical calculations, magnetic relaxation in 1 is single-ion in origin and takes place through the first excited state of each DyIII ion. When using the succinato dicarboxylate bridging ligand instead of acetate, compounds 2 and 3 were serendipitously formed, which have a closed structure with the succinate anion bridging two ZnDy subunits belonging to two different ligands. It should be noted that only compound 2 exhibits slow relaxation of magnetization in the absence of an external magnetic field. According to experimental and theoretical data, 2 relaxes through the second excited Kramers doublet (Ueff = 342 K). In contrast, 3 displays field-induced SMM behaviour (Ueff = 203 K). However, the Co/Zn diluted version of this compound 3Zn shows slow relaxation at zero field (Ueff = 347 K). Ab initio theoretical calculations clearly show that the weak ferromagnetic coupling between CoII and DyIII ions is at the origin of the lack of slow relaxation of this compound at zero field. Compound 2 and its diluted analogues 2Y and 3Zn show hysteresis loops at very low temperature, thus confirming their SMM behaviour. Finally, compounds 1 and 2 show DyIII based emission even at room temperature that, in the case of 2, allows us to extract the splitting of the ground 6H15/2 term, which matches reasonably well with theoretical calculations.en
dc.description.sponsorshipThis work was developed within the scope of the projects given by the Spanish Ministry of Science, Innovation and Universities (MCN/AEI/FEDER, UE) (PGC2018-102052-A-C22, PGC2018-102052-B-C21, MCIN/ AEI /10.13039/501100011033/ FEDER "Una manera de hacer Europa"), the University of the Basque Country (GIU 20/028), Gobierno Vasco/Eusko Jaurlaritza (IT1755-22), Red Guipuzcoana de Ciencia, Tecnología e Innovación (FA385/2023, DG23/16) and Junta de Andalucía (FQM-195, FQM-394, A-FQM-172-UGR18 and B-FQM-734-UGR20 and ProyExcel_00386). This work was partly supported by GIMRT and ICC-IMR programs of the Institute for Materials Research, Tohoku University. ALO agradece el apoyo financiero de las becas PID2021-122613OB-I00 financiadas por MCIN/AEI/ 10.13039/501100011033 y PJUPNA2020 de la Universidad Pública de Navarra.
dc.format.mimetypeapplication/pdfen
dc.identifier.citationZabala-Lekuona, A., Lopez de Pariza, X., Díaz-Ortega, I. F., Cepeda, J., Nojiri, H., Gritsan, N. P., Dmitriev, A. A., López-Ortega, A., Rodríguez-Diéguez, A., Seco, J. M., Colacio, E. (2024) From field-induced to zero-field SMMs associated with open/closed structures of bis(ZnDy) tetranuclear complexes: a combined magnetic, theoretical and optical study. Dalton Transactions, 53(18), 7971-7984. https://doi.org/10.1039/d4dt00148f.
dc.identifier.doi10.1039/d4dt00148f
dc.identifier.issn1477-9226
dc.identifier.urihttps://academica-e.unavarra.es/handle/2454/50650
dc.language.isoeng
dc.publisherRoyal Society of Chemistry
dc.relation.ispartofDalton Transactions, 2024, 53(18), 7971-7984
dc.relation.publisherversionhttps://doi.org/10.1039/d4dt00148f
dc.rightsThis article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
dc.rights.accessRightsinfo:eu-repo/semantics/openAccess
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subjectMannich base liganden
dc.subjectTetranuclear complexesen
dc.subjectMagnetic relaxationen
dc.subjectSMM behaviour (Single-Molecule Magnet)en
dc.subjectDyIII based emissionen
dc.titleFrom field-induced to zero-field SMMs associated with open/closed structures of bis(ZnDy) tetranuclear complexes: a combined magnetic, theoretical and optical studyen
dc.typeinfo:eu-repo/semantics/article
dc.type.versioninfo:eu-repo/semantics/publishedVersion
dspace.entity.typePublication
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relation.isAuthorOfPublication.latestForDiscoveryc295cba6-cd13-4ee7-accd-0a1d5266c972

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