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Synthesis, Structure And Magnetism Of 3D Or 3D-4F Clusters

Posted on:2010-03-23Degree:MasterType:Thesis
Country:ChinaCandidate:Y N WangFull Text:PDF
GTID:2121360278967743Subject:Inorganic Chemistry
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Eleven single crystals were obtained by reactions of metal salts with three ligands,in which structures of seven crystals were determined by X-ray single diffraction.The three ligands include two kinds of tridentate ligands including H2L1(N-(2-hydroxybenzyl)-1,1-dimethyl ethanolamine and H2L2(salicylidene-2-amino-2-methyl-1-propanol), and one tetradentate ligand:H2L3(salicylidene-N-(2-hy droxyethyl)ethylenediamine).The formula of seven compounds are as following: compound 1: [Ni(HL1)2]·(CH3OH)2(H2O) compound 2: [{Cu2(L1)2(CH3OH)2} {[Cu2(HL1)(H2O)2](ClO4)2}] compound 3: [Mn2ⅢMnⅡ(L2)2(CH3COO)4(H2O)2]·2H2O compound 4: [Mn4Ⅲ(L2)4(μ-1,1-N3)(μ3 -O)(H2O)2]ClO4 compound 5: [Mn2ⅢNi2Ⅱ(L2)2(sal)2(CH3COO)2(μ3-OCH3)2]·CH3OH compound7:[Co4ⅢGd2Ⅲ(L2)4(μ3-OCH3)2(μ-OCH3)2((μ-O2CCH3)6(CH3OH)2] compound 8: [Cu(HL3)(ClO4)]2Structure analysis suggest that the structures of these seven new compounds display novel structures.Coordination compound 1 consists of mono-nuclear nickel structure,and abundant hydrogen bonding interactions between neighboring nickel units form the 1D chain-like supermolecule;Compound 2 is the first [2×1+2×1] type of cocrystal in transition metal coordination compounds.Two crystallographic independent units {Cu2(L1)(CH3OH)2}and {[Cu2(HL1)(H2O)2](ClO4)2} are crystallized in the same unit cell. Coordination compound 3 contains mixed-valence linear trinuclear Mn clusters,and in each cluster bond angle during the three Mn ions is strictly 180°;Coordination compound 4 is a homo-metal tetranuclear cluster with only one azido .The four Mn ions form a tetrahedron core ,and only exclusive azide bridges two Mn ions in EO model ,and all the four ligands,L2-, usingη1:η1:η1:μ-coordination model to bridge the four Mn ions. The structure of coordination compound 5 contains tetranuclear Mn-Ni hetero-metal clusters. The metal ions and oxygen atoms from ligands form a defective double cube-like framework of the cluster .Coordination compound 7 is a novel hexanuclear 3d-4f hetero-metal cluster with a dumbbell-like structure.The two defective cube constitute the two ends of dumbbell.Two acetic ions using rareη1:η2: u-coordination model bridge Gd ions from the two defective cube to form the handle of dumbbell.Coordination compound 7 is also the first hexanuclear Co-Gd 3d-4f hetero-metal cluster. Coordination compound 7 consists of 1D helix chain-like structures composed of perchlorate ions bridging mono-nuclear Cu unit. Magnetic measurements indicate all Mn ions in coordination compound 3 and 4 are antiferromagnetically coupled,but the behaviorof χмT under low temperature suggests coordination compound 4 may be a single molecule magnet. Magnetic measurements indicate coordination compound 5 is antiferromagnetic interaction between Ni2+ and Mn2+ ,and Coordination compound 7 displays paramagnetism behavior of Gd3+.
Keywords/Search Tags:clusters, magnetic properties, crystal structure, cocrystal, 3d-4f
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