New Mixed-Valence Mn-6(II/III) Complexes Bearing Oximato and Azido Ligands: Synthesis, and Structural and Magnetic Characterization

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dc.contributor.authorLampropoulos, C.en
dc.contributor.authorStamatatos, T. C.en
dc.contributor.authorManos, M. J.en
dc.contributor.authorTasiopoulos, A. J.en
dc.contributor.authorAbboud, K. A.en
dc.contributor.authorChristou, G.en
dc.date.accessioned2015-11-24T16:42:38Z
dc.date.available2015-11-24T16:42:38Z
dc.identifier.issn1434-1948-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/8576
dc.rightsDefault Licence-
dc.subjectmixed-valent compoundsen
dc.subjectpolynuclear complexesen
dc.subjectmanganeseen
dc.subjectazidesen
dc.subjectmagnetic propertiesen
dc.subjectsingle-molecule magnetsen
dc.subjecthigh-spin moleculesen
dc.subjectmanganese cluster chemistryen
dc.subject2-pyridyl ketone oximeen
dc.subjecthigh-nuclearity cagesen
dc.subjectground-stateen
dc.subjectcrystal-structureen
dc.subjectmetal-clustersen
dc.subjectpyridyl oximesen
dc.subjectphotosystem-iien
dc.titleNew Mixed-Valence Mn-6(II/III) Complexes Bearing Oximato and Azido Ligands: Synthesis, and Structural and Magnetic Characterizationen
heal.abstractThe combined use of the anion of methyl 2-pyridyl ketone oxime (mpko(-)) and azides (N-3(-)) in non-carboxylate Mn chemistry has afforded two new Mn-6 clusters, [Mn6O3(N-3)(3)-(mpko)(6)(H2O)(3)](ClO4)(2) (1) and [Mn(6)O3(N-3)(5)(mpko)(6)(H2O)] (2), which are mixed-valence (Mn-II, 5 Mn-III). The 1:1:1:1 reaction of Mn(ClO4)(2)center dot 6H(2)O, mpkoH, NaN3 and NEt3 in MeOH gave the cationic complex 1, while a similar reaction using additional NaO2CMe led instead to the neutral complex 2. The structurally unprecedented cores of the two cages are very similar, and contain the six Mn ions in a topology comprising three vertex-sharing oxide-centered triangles bridged by two end-on azides. Variable-temperature, solid-state dc and ac magnetization studies were carried out for 1 and 2 in the 1.8-300 K range. The data reveal S = 5/2 ground states for both complexes, and fitting of magnetization vs. field (H) and temperature (T) data by matrix diagonalization for 1 gave S = 5/2, D = -1.4(3) cm(-1), and g = 1.99(1), where D is the axial zero-field splitting (ZFS) parameter. The combined results demonstrate the versatility of 2-pyridyl ketone oxime anions in the presence of suitable ancillary ligands, such as azides, for the synthesis of new Mn clusters, without requiring the co-presence of carboxylate ligands.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDOI 10.1002/ejic.200901013-
heal.identifier.secondary<Go to ISI>://000278611600005-
heal.identifier.secondaryhttp://onlinelibrary.wiley.com/store/10.1002/ejic.200901013/asset/2244_ftp.pdf?v=1&t=hmu92nij&s=d025477909ee44e3cb9034c818e913eb10be3395-
heal.journalNameEuropean Journal of Inorganic Chemistryen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2010-
heal.publisherWiley-VCH Verlagen
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

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