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Thiodiacetate-Manganese Chemistry with N ligands: Unique Control of the Supramolecular Arrangement over the Metal Coordination Mode.

hal.structure.identifierQuimica Inorganica
hal.structure.identifierInstituto de Tecnología Química
dc.contributor.authorGRIRRANE, Abdessamad
hal.structure.identifierQuimica Inorganica
dc.contributor.authorPASTOR, Antonio
hal.structure.identifierQuimica Inorganica
dc.contributor.authorGALINDO, Agustín
hal.structure.identifierInstituto de Investigaciones Químicas
dc.contributor.authorALVAREZ, Eleuterio
hal.structure.identifierIstituto di Chimica dei Composti Organometallici [ICCOM]
dc.contributor.authorMEALLI, Carlo
hal.structure.identifierIstituto di Chimica dei Composti Organometallici [ICCOM]
dc.contributor.authorIENCO, Andrea
hal.structure.identifierIstituto di Chimica dei Composti Organometallici [ICCOM]
dc.contributor.authorORLANDINI, Annabella
hal.structure.identifierInstitut de Chimie de la Matière Condensée de Bordeaux [ICMCB]
hal.structure.identifierDipartimento di Chimica & CNR-INSTM [LAMM]
dc.contributor.authorROSA, Patrick
hal.structure.identifierDipartimento di Chimica & CNR-INSTM [LAMM]
dc.contributor.authorCANESCHI, Andrea
hal.structure.identifierLaboratoire national des champs magnétiques intenses - Grenoble [LNCMI-G]
dc.contributor.authorBARRA, Anne-Laure
hal.structure.identifierDepartamento de Química Física
dc.contributor.authorSANZ, Javier Fernández
dc.date.issued2011
dc.identifier.issn0947-6539
dc.description.abstractEnCompounds based on the Mn-tda unit (tda=S(CH(2) COO)(2) (-2) ) and N co-ligands have been analyzed in terms of structural, spectroscopic, magnetic properties and DFT calculations. The precursors [Mn(tda)(H(2) O)](n) (1) and [Mn(tda)(H(2) O)(3) ]⋅H(2) O (2) have been characterized by powder and X-ray diffraction, respectively. Their derivatives with bipyridyl-type ligands have formulas [Mn(tda)(bipy)](n) (3), [{Mn(N-N)}(2) (μ-H(2) O)(μ-tda)(2) ](n) (N-N=4,4'-Me(2) bipy (4), 5,5'-Me(2) bipy, (5)) and [Mn(tda){(MeO)(2) bipy}⋅2 H(2) O](n) (6). Depending on the presence/position of substituents at bipy, the supramolecular arrangement can affect the metal coordination type. While all the complexes consist of 1D coordination polymers, only 3 has a copper-acetate core with local trigonal prismatic metal coordination. The presence of substituents in 4-6, together with water co-ligands, reduces the supramolecular interactions and typical octahedral Mn(II) ions are observed. The unicity of 3 is also supported by magnetic studies and by DFT calculations, which confirm that the unusual Mn coordination is a consequence of extended noncovalent interactions (π-π stacking) between bipy ligands. Moreover, 3 is an example of broken paradigm for supramolecular chemistry. In fact, the desired stereochemical properties are achieved by using rigid metal building blocks, whereas in 3 the accumulation of weak noncovalent interactions controls the metal geometry. Other N co-ligands have also been reacted with 1 to give the compounds [Mn(tda)(phen)](2) ⋅6 H(2) O (7) (phen=1,10-phenanthroline), [Mn(tda)(terpy)](n) (8) (terpy=2,2':6,2''-terpyridine), [Mn(tda)(pyterpy)](n) (9) (pyterpy=4'-(4-pyridyl)-2,2':6,2''-terpyridine), [Mn(tda)(tpt)(H(2) O)]⋅2 H(2) O (10) and [Mn(tda)(tpt)(H(2) O)](2) ⋅2 H(2) O (11) (tpt=2,4,6-tris(2-pyridyl)-1,3,5-triazine). Their identified mono-, bi- or polynuclear structures clearly indicate that hydrogen bonding is variously competitive with π-π stacking.
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.title.enThiodiacetate-Manganese Chemistry with N ligands: Unique Control of the Supramolecular Arrangement over the Metal Coordination Mode.
dc.typeArticle de revue
dc.identifier.doi10.1002/chem.201100988
dc.subject.halChimie/Matériaux
bordeaux.journalChemistry - A European Journal
bordeaux.page10600-10617
bordeaux.volume17
bordeaux.issue38
bordeaux.peerReviewedoui
hal.identifierhal-00626089
hal.version1
hal.popularnon
hal.audienceInternationale
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00626089v1
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