Synthesis,Structures And Properties Of Coordination Clusters Based On Schiff Base

In this thesis,we explore the synthesis,structures and properties of 3d-4fheterometallic coordination clusters.Twenty-two clusters were prepared by the reactions of transion and rare earth metal salts with three key Schiff base ligands,including pentadentate mono-Schiff base H₃L¹[o-vanillin-3-amino-1,2-propanediol,sexadentate symmetric bis-Schiff base H₂L²[o-vanillin-hydrazine hydrate]and sexadentate asymmetric bis-Schiff base HL³[（o-vanillin-3（2-pyridyl）-amidrazone）].All the complexes were characterized by IR,UV-Vis and PXRD.Thirteen of the complexes were tested by single crystal X-ray diffraction,and cell parameters of the other nine complexes were obtained.The formulas are as follows:1:[Zn（H₂L¹）₂]2-7:[Ni₆Ln₂（μ₃-OL¹）₂（HL¹）₂（μ₃-OCH₃）₄（μ-OHCH₃）₄（NO₃）₄（CH₃CN）₂]·CH₃CN·H₂O[Ln=Gd（2）,Dy（3）,Tb（4）,Ho（5）,Er（6）,Eu（7）]8-13:[Fe₂Ln₂L₂¹（μ₃-OH₂）₂（paba）₂（NO₃）₄][Ln=Sm（8）,Eu（9）,Nd（10）,Pr（11）,La（12）,Ce（13）]14-19:{[Zn₂Ln₂L₄²（N₃）₂]·[Zn₂Ln₂L₄²（N₃）Cl]·3C₂H₅OH}[Ln=Eu（14）,Tb（15）,Sm（16）,Dy（17）,Er（18）,Yb（19）]20:[Zn（HL³）Cl₂]21-22:[M₄L₂³L²（OAc）₂（SCN）₂][M=Zn（21）,Cu（22）]Complexes 2-7 are isostructural octanuclear[Ni₆Ln₂]3d-4f heterometallic clusters.The Ln³⁺ion is eight-coordinated and adopts the distorted trigondodecahedral geometry.Ni²⁺ion is six-coordinated to form an irregular octahedral geometry.The metal center[Ni₆Ln₂O₁₀]forms a deck chair-like skeleton.Complexes 8-13 are isomorphic tetranuclear[Fe₂Ln₂]3d-4f heterometallic clusters.The[Fe₂Ln₂O₆]can be described in a terms of defect-dicubane（or butterfly topology）.Fe³⁺ion is six-coordinated and adopts a distorted octahedral geometry,and The Ln³⁺ion is s ten-coordinated,displaying distorted bicapped square antiprismatic geometry,and the BET and pore size of complexes 8-11 have been measuredComplexes 14-19 are isomorphic octanuclear[Zn₄Ln₄]3d-4f heterometallic clusters.The structure consists of two basic units withπ-πstacking interactions.The luminescent emission spectram of complexes 14-17 have been studied.Complexes 1,20 are mononuclear zinc complex.Complexes 21 and 22 are isomorphic tetranuclear clusters,and the fluorescence properties of complexes 1 and21 were determined.