Study On Synthesis, Structures And Properties Of Novel Heterometallic Clusters

Due to its magnetic and optical properties,heterometallic clusters have potential applications in advanced functional molecular materials.M^?-Ln^?? heterometallic clusters are an important part of functional complex materials.The purpose of this thesis is to design and synthesize heterometallic clusters with stable structure and excellent performance.A series of Zn^?-Ln^?heterometallic clusters were synthesized at room temperature by selecting novel Salen-type ligands,transition Zn ^? ion salts and Ln^?ion metal salts with different flexible arms.The structure of Zn^?-Ln^?? heterometallic clusters characterized by X-ray diffraction,IR spectroscopy and elemental analysis.Fluorescence spectroscopy and magnetic properties were also studied.Furthermore,the structure-activity relationship of the obtained Zn^?-Ln ^?? heterometallic clusters was investigated.The research of this thesis is divided into the following four chapters:Chapter 1:The progress in synthesis,magnetics and luminescence of M^?-Ln^?,especially Zn^?-Ln ^?? heterometallic clusters is reviewed herein.On this basis,the purpose and significance of this thesis is described.Chapter2:ThetargetligandH₃L^?:1-?2-Hydroxy-3-methoxy-benzoylamino?-2-?2-hydroxy-benzylideneamino?2-propanol,has been synthesized.Three isomorphic complexes of[Ln₂Zn₈L₂^??OH?₄?OAc?₁₂]?CH₃OH?H₂O,Ln=Nd?1?,Pr?2?,La?3?were obtained in a mixed solvent system of acetonitrile and methanol.Polycrystalline samples of Zn^?-Tb^??Zn^?-Dy ^??Zn^?-Er ^??Zn^?-Yb^?complexes of this ligand were also obtained.The NIR luminescence and magnetic properties of some complexes were investigated.Chapter3:ThetargetligandH₂L^?:1-?2-Hydroxy-3-methoxy-benzoylamino?-2-?2-hydroxy-3-methoxy-benzylideneamino?-propane,has been synthesized.The complex[Zn₄L₃^??OH??NO₃?]?H₂O has also been obtained.The complex can effectively recognize H₂PO₄^-as an anion probe in the system of DMSO:H₂O?V:V?=9:1.In addition,the complex Eu₂Zn₄L₄^??OAc?₆ was obtained by using H₂L^? and Zn?NO₃?₂ and EuCl₃ in a mixed solvent system of methanol and acetonitrile.Chapter4:ThetargetligandH₂L^?:1-?2-Hydroxy-benzoylamino?-2-?2-hydroxy-4-nitro-benzylideneamino?-bis?2-ethoxy?-ethane,has been synthesized.Five isomorphic Zn^?-Ln ^?? clusters with molecular formula of[Ln₂Zn₃L₄^??NO₃?₄]?2H₂O,Ln=Tb?1?;Eu?2?;Dy?3?;Nd?4?;Er?5?have been obtained.Photophysical determination indicates that the ligand can effectively sensitize Eu^?? and Tb^?? characteristic luminescence.The fluorescence of different systems was measured by changing the order of ion addition.It is preliminarily concluded that in acetonitrile the H₂L^?-Zn^? is more effective for sensitization of Tb^?.