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Coexistence of intramolecular ligand-mediated and through hydrogen-bond magnetic interactions in a chain of dicopper(II) units

hal.structure.identifierDepartament de Química Inorganica
dc.contributor.authorCOSTA, José Sánchez
hal.structure.identifierLaboratoire de Chimie - UMR5182 [LC]
dc.contributor.authorBANDEIRA, Nuno
hal.structure.identifierLaboratoire de Chimie - UMR5182 [LC]
dc.contributor.authorLE GUENNIC, Boris
hal.structure.identifierLaboratoire de Chimie - UMR5182 [LC]
hal.structure.identifierLaboratoire de chimie quantique et de modélisation moléculaire [LCQMM]
dc.contributor.authorROBERT, Vincent
hal.structure.identifierDepartament de Química Inorganica
hal.structure.identifierInstitució Catalana de Recerca i Estudis Avançats = Catalan Institution for Research and Advanced Studies [ICREA]
dc.contributor.authorGAMEZ, Patrick
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
dc.contributor.authorCHASTANET, Guillaume
hal.structure.identifierCentro de Investigacion y Desarrollo Tecnologico en Electroquímica
dc.contributor.authorORTIZ-FRADE, Luis
hal.structure.identifierFacultad de Química
dc.contributor.authorGASQUE, Laura
dc.date.issued2011
dc.identifier.issn0020-1669
dc.description.abstractEnThe reaction of 2,8-dimethyl-5,11-bis(pyridin-2-ylmethyl)-1,4,5,6,7,10,11,12-octahydroimidazo[4,5-h]imidazo[4,5-c][1,6]-diazecine (dimp) with copper(II) nitrate in water produces the compound [Cu(2)(dimp)(H(2)O)(2)(NO(3))(2)](NO(3))(2). The single-crystal X-ray structure shows the formation of hydrogen-bonded chains in the lattice that are formed by dicopper(II) units doubly connected by nitrate/water bridges. Within the one-dimensional chains, the Cu ions are separated by either intramolecular or intermolecular distances of 7.309(2) Å or 6.255(2) Å, respectively. The magnetic susceptibility data revealing weak antiferromagnetic exchange interactions between the copper(II) ions were interpreted by considering two possible models, namely, an isolated dinuclear and a 1-D chain picture. The latter leads to an alternation J(1) = -11.6 and J(2) = -3.0 cm(-1) along the chain. In order to clarify the relative strengths of the exchange couplings through hydrogen bonds and via the bridging dimp ligand, solution EPR studies and quantum chemical calculations were carried out. EPR studies unambiguously conclude on the existence of an exchange interaction J(a) mediated by the dinucleating dimp ligand, while the through-H coupling J(b) is physically absent in solution. On the basis of dinuclear units extracted from the X-ray data, J(a) was estimated around -5.0 cm(-1) from DFT-based calculations (M06 functional), whereas J(b) is negligible. In contrast, wave function configuration interaction calculations (DDCI) support a description where both inter- and intramolecular pathways coexist with a preeminent role of H bonds with J(a) = -2.8 and J(b) = -10.4 cm(-1). Not only are these values very consistent with the extracted set of parameters (J(1), J(2) = -11.6, -3.0 cm(-1)) but the possibility to generate leading exchange coupling through weak bonds is evidenced by means of wave function-based calculations.
dc.language.isoen
dc.publisherAmerican Chemical Society
dc.title.enCoexistence of intramolecular ligand-mediated and through hydrogen-bond magnetic interactions in a chain of dicopper(II) units
dc.typeArticle de revue
dc.identifier.doi10.1021/ic200480d
dc.subject.halChimie/Matériaux
bordeaux.journalInorganic Chemistry
bordeaux.page5696-5705
bordeaux.volume50
bordeaux.issue12
bordeaux.peerReviewedoui
hal.identifierhal-00602029
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00602029v1
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