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dc.contributor.authorGil García, Rubén 
dc.contributor.authorMadariaga, Gotzon
dc.contributor.authorJiménez Pérez, Alondra 
dc.contributor.authorHerrán Torres, Ignacio
dc.contributor.authorGago González, Adrián
dc.contributor.authorUgalde, María 
dc.contributor.authorJanuskaitis, Vaidas
dc.contributor.authorBarrera García, Joaquín
dc.contributor.authorInsausti, Maite
dc.contributor.authorGalletero, María S.
dc.contributor.authorBorrás, Joaquín
dc.contributor.authorCuevas Vicario, José Vicente 
dc.contributor.authorPedrido Castiñeiras, Rosa
dc.contributor.authorGómez Sáiz, Patricia
dc.contributor.authorLezama, Luis
dc.contributor.authorGarcía Tojal, Javier 
dc.date.accessioned2024-07-01T06:55:06Z
dc.date.available2024-07-01T06:55:06Z
dc.date.issued2023-03-06
dc.identifier.urihttp://hdl.handle.net/10259/9323
dc.description.abstractThe use of perchlorate ancillary ligands with relatively low coordination ability nicely illustrates a rich structural diversity in thiosemicarbazone copper(II) (TSC-Cu(II)) systems. Five compounds with the formulae {[CuL(OH2)][CuL(OClO3)]}n·nClO4·2nH2O (1), [{CuL(OClO3)}2] (2), [Cu(HL)(OClO3)2(OH2)] H2O (3), [Cu2L3](ClO4)·2H2O (4) and [Cu(HL)(NCS)](ClO4) (5) are studied, where HL = pyridine-2-carbaldehyde thiosemicarbazone. The crystal structures show the presence of polynuclear species in the compounds containing an anionic L− thiosemicarbazone ligand: 1D chains (1) and dinuclear (2 and 4) arrangements. Meanwhile, complexes with a neutral HL ligand give rise to mononuclear entities (3 and 5). The chemical and structural parallelism of these complexes with the analogous TSC–Cu(II)–nitrate system is discussed. The thiocyanate ligand in compound 5 comes from partial desulfurization of the thiosemicarbazone in acid medium and results in an incommensurate modulated structure. On the other hand, it is proposed that [Cu2L3]+ species present in 4 could play a possible role in desulfurization reactions. Experimental evidence and theoretical calculations support a proposed mechanism for the partial desulfurization of preformed TSC-Cu(II) entities in basic and physiological media to yield the [CuL(LCN)] (HLCN = pyridine-2-ylmethylene(hydrazine carbonitrile)) and [{CuL(SH)}2)] compounds.en
dc.description.sponsorshipThis work was supported by the European Union H2020-LC-SC3-2020-NZE-RES-CC, NMBP-16- 2020-GA 953152 and DT-NMBP-04-2020 Projects, together with Ministerio de Ciencia, Innovación, for the project PID2021- 127531NB-I00 (AEI/10.13039/501100011033/FEDER, UE), PDC2022-133955-I00 and Ministerio de Ciencia, Innovación y Universidades CTQ(QMC) RED2018-102471-T MultiMetDrugs Network (Spain), Consejería de Educación of Junta de Castilla y León and FEDER BU049P20, Fundacion Bancaria Caixa D. Estalvis i Pensions de Barcelona 001 and Ministerio de Ciencia e Innovación PID2019-106644GB-I00 and Gobierno Vasco IT1458-22. R. G.-G. and A. J.-P. wish to thank the Junta de Castilla y León for their Doctoral Fellowships.en
dc.format.mimetypeapplication/pdf
dc.language.isoenges
dc.publisherRoyal Society of Chemistryen
dc.relation.ispartofCrystEngComm. 2023, V. 25, n. 15, p. 2213-2226en
dc.rightsAtribución 4.0 Internacional*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subject.otherQuímica inorgánicaes
dc.subject.otherChemistry, Inorganicen
dc.titlePerchlorate-induced structural diversity in thiosemicarbazone copper(ii) complexes provides insights to understand the reactivity in acidic and basic mediaen
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.relation.publisherversionhttps://doi.org/10.1039/D3CE00119Aes
dc.identifier.doi10.1039/D3CE00119A
dc.identifier.essn1466-8033
dc.journal.titleCrystEngCommen
dc.volume.number25es
dc.issue.number15es
dc.page.initial2213es
dc.page.final2226es
dc.type.hasVersioninfo:eu-repo/semantics/publishedVersiones


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