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Cyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clusters

dc.contributor.authorAlexandropoulos, Dimitris I.en
dc.contributor.authorMoushi, Eleni E.en
dc.contributor.authorPapatriantafyllopoulou, Constantinaen
dc.contributor.authorBeavers, Christine M.en
dc.contributor.authorTeat, Simon J.en
dc.contributor.authorTasiopoulos, Anastasios J.en
dc.contributor.authorChristou, Georgeen
dc.contributor.authorStamatatos, Theocharis C.en
dc.creatorAlexandropoulos, Dimitris I.en
dc.creatorMoushi, Eleni E.en
dc.creatorPapatriantafyllopoulou, Constantinaen
dc.creatorBeavers, Christine M.en
dc.creatorTeat, Simon J.en
dc.creatorTasiopoulos, Anastasios J.en
dc.creatorChristou, Georgeen
dc.creatorStamatatos, Theocharis C.en
dc.date.accessioned2019-11-21T06:16:19Z
dc.date.available2019-11-21T06:16:19Z
dc.date.issued2016
dc.identifier.urihttp://gnosis.library.ucy.ac.cy/handle/7/55246
dc.source.urihttps://nls.ldls.org.uk/welcome.html?ark:/81055/vdc_100031730199.0x000036
dc.subjectAnorganische chemieen
dc.subjectChemistry, Inorganicen
dc.subjectChimie inorganiqueen
dc.subjectOrganometaalverbindingenen
dc.subjectPériodiquesfr
dc.titleCyanate groups in higher oxidation state metal cluster chemistry: Mixed-valence (II/III) Mn16 and Mn18 clustersen
dc.typeinfo:eu-repo/semantics/article
dc.author.faculty002 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied Sciences
dc.author.departmentΤμήμα Χημείας / Department of Chemistry
dc.type.uhtypeArticleen
dc.description.notes<p>ID: 1135en
dc.description.notesIn: Polyhedron, 131-142.en
dc.description.notesSummary: Graphical abstractThe combination of cyanate, carboxylate and 2-(hydroxymethyl)pyridine ligands in higher oxidation state Mn cluster chemistry has led to two different families of MnII/III16and MnII/III18clusters with interesting topologies and nanoscale dimensions.AbstractThe employment of cyanato (OCN−) group in high oxidation state manganese cluster chemistry, in conjunction with carboxylate ions and the organic chelating/bridging ligand 2-(hydroxymethyl)pyridine (hmpH), is reported. The syntheses, crystal structures, and magnetochemical characterization are described for [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)) and [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). The 2:1:1:1 reactions of Mn(O2CMe)2·4H2O, hmpH, NaOCN and NEt3in solvent MeOH or EtOH afford the isostructural complexes [Mn16O8(OR)4(OCN)4(O2CMe)12(hmp)6(ROH)2] (R = Me (1), Et (2)). The [Mn16(μ4-O)4(μ3-O)4(μ-OMe)4(μ3-OR)6(μ-OR)6]10+core of representative complex1comprises a MnII4MnIII4double-cubane subunit attached on either side to two symmetry-related MnIIMnIII3defective dicubanes. A similar reaction of Mn(O2CR)2·4H2O, hmpH, NaOCN and NEt3, but in solvent MeCN, led instead to the formation of [Mn18O14(O2CR)18(hmp)4(hmpH)2(H2O)2] (R = Me (3), Et (4)). Compounds3and4are very similar to each other and can be described as a central [MnIII4(μ-O)6] rodlike subunit attached on either side to two symmetry-related [Mn7O9] subunits. Variable-temperature, solid-state dc and ac magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions in all compounds, and possibleS = 2 or 1 (for1and2) andS = 0 (for3and4) ground state spin values. The combined results demonstrate the ability of cyanato groups to facilitate the formation of new polynuclear MnII/IIIcomplexes with structures different than these obtained from the use of the related azides.</p>en
dc.contributor.orcidTasiopoulos, Anastasios J. [0000-0002-4804-3822]
dc.contributor.orcidAlexandropoulos, Dimitris I. [0000-0002-8759-9495]
dc.contributor.orcidPapatriantafyllopoulou, Constantina [0000-0002-5652-7747]
dc.contributor.orcidStamatatos, Theocharis C. [0000-0002-9798-9331]
dc.gnosis.orcid0000-0002-4804-3822
dc.gnosis.orcid0000-0002-8759-9495
dc.gnosis.orcid0000-0002-5652-7747
dc.gnosis.orcid0000-0002-9798-9331


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