Studies On The Synthesis,Structure And Properties Of Transition Metal Complexes Of Schiff Bases Condensed From Acenaphthenequinone Monooxime With Aminoalcohol

Polynuclear complexes have attracted much attention of many chemists for their interesting novel structures and fascinating magnetic properties.In this paper,we used aromatic Schiff bases containing oxime and hydroxyl groups as ligands to synthesize highnuclear complexes with oxime or hydroxyl linkers for further magnetic studies.Eleven new transition metal complexes were separated from the reactions of the designed ligands with different transition metal salts,which include seven transition metal complexes of a Schiff base（H₂L²）condensed from acenaphthenequinone monoxime with2-amino-1-propanol and and four transition metal complexes of another Schiff base（H₂L³）condensed from acenaphthenequinone monoxime with 2-aminoethanol.Their structures were characterized by elemental analysis,IR spectroscopy,powder X-ray diffractional analysis and single crystal X-ray diffraction analysis.Their magnetic properties were also investigated systematically.The main work is presented below:1.[Mn^IIIMn^IIL²（HL²）Cl₂（CH₃CN）]（1）and[Mn₂^IIIMn₂^II（L³）₂（HL³）₂Cl₄（CH₃OH）₂]（2）were separated from the reactions of H₂L² and H₂L³ with Mn Cl₂·4H₂O,respectively.Complex 1 is a dinuclear mixed-valence manganese complex with mixed state.The Mn（II）and Mn（III）ions in complex 1 are five-coordinated in trigonal bipyramidal and square pyramidal geometries,respectively.Complex 2 is a two-layered tetranuclear manganese complex.Each layer of 2 is formed by the connection of one Mn（III）and one Mn（II）through one oxime group and one hydroxyl group from one（L³）^2-and one（HL³）^-,repespectively.The two layers are further connected through the connection of the two Mn（III）ions by two oximato oxygen atoms,formimg a double-layered tetranuclear structure.The magnetic properties of complexes 1 and 2 were measured.The results showed that complex 1 and 2 exhibit dominant antiferromagnetic behavior.2.The reactions of H₂L² or H₂L³ with Ni（Cl O₄）₂·6H₂O or Ni（OAC）₂·6H₂O gave[Ni₂L²（HL²）（THF）₄]（Cl O₄）·THF（3）,[Ni₆（μ₃-OH）₃L²（HL²）₆（H₂L²）]（Cl O₄）·2H₂O（4）,[Ni₃（HL²）₆]·CH₃CN（5）,[Ni₃（μ₃-OH）（HL²）₃（OAC）₂（DMF）]·H₂O（6）,[Ni₁₂（μ₃-OH）₄（HL³）₁₂（CO₃）₂（OAC）₄（H₂O）₂]·12H₂O（7）and[Ni₆（μ₃-OH）₂（HL³）₆（OAC）₄]（8）,respectively.Co mplex 3 is a dinuclear nickel complex.Complex 4 is a hexanuclear nickel complex,in which the six nickel atoms are connected by threeμ₃-OH^-ions.Complex 5 is a t rinuclear nickel complex,in which the three Ni atoms are six-coordinated indistorted octahedral geometries and are connected by six（HL²）^-ligands to form a crown-lik e skeleton.Complex 6 is a trinuclear nickel complex with the three nickel atoms in one plane.The three Ni atoms in complex 6 are connected through oneμ₃-OH^-,one acetate anion and three oxime groups from three（HL²）^-ligands.Complex 7 is a do decanuclear nickel cluster which is constructed from two hexanuclear Ni₆ units by th e linkage of（HL³）^-ligands.The hexanuclear Ni₆ unit of 7 is formed from two plan ar trigonal Ni₃ units by the hydroxyl alkyl imino moiety and one CO₃^2-anion.Comp lex 8 is a double-layered hexanuclear nickel cluster which is formed from the conne ction of two planar trigonal Ni₃ units by the hydroxyl alkyl imino moieties of（HL³）^-ligands.The magnetic properties of complexes 3,5,6,7 and 8 were investigated.The results showed that five complexs exhibit dominant antiferromagnetic interactions between the metal ions in these complexes.3.[Cu₂（HL²）₂（Cl O₄）₂]·2Diox（9）,[Cu₁₂（μ₄-O）₄（HL²）₁₂（CO₃）₂（Et OH）₂]·6Et OH（10）and[Cu₂L³（HL³）Cl]（11）were separated from the reactions of H₂L² and H₂L³ with Cu（Cl O₄）₂·6H₂O,Cu（NO₃）₂·3H₂O and Cu（OAC）₂·H₂O,respectively.Complex 9 and 11 are both dinuclear copper complexes with the two copper atoms and the main skeletons of the two Schiff bases in one plane.Complex 10 is a four-layered dodecanuclear copper cluster in which each layer has an Ocentered planar trigonal skeleton.The upper two layers of 10,as well as the lower two layers,are further linked by the oxo ligands.The middle two layers of10 are conneted by the hydroxyl alkyl imino moieties of（HL²）^-ligands,leading to the construction of the four-layered dodecanuclear copper cluster.The magnetic measurement of complex 10 showed that it exhibits dominant antiferromagnetic behavior between the metal ions in this complexes.