Synthesis And Characterization Of Heterometallic Complex Using Metallo-Ligand As Building Block

In recent years, heterometallic coordination compounds has sparked tremendous interest for chemists due to their potential applications in catalysis, gas adsorption, luminescence, magnetism material, as well as their fascinating topologies. Therefore, further understanding the rules of structure and synthesis of heteronuclear coordination compounds and the application has become the aim for chemists to explore.Using metallo-ligand to construct heterometallic compounds has received extensive attention for their intriguing architectures. One of important strategy for preparing heteronuclear complexes is the forming of the Schiff base. The Schiff base ligands which is derived from the condensation of salicylaldehyde or its derivatives with amino acid have strong capability of coordination, various coordination modes and mixed-donor atoms which have highly electronegative and can provide unshared pair electrons. Terminal oxygen atoms which are from carboxylate and carbonyl can coordinate to other metal ions. The design and synthesis of such materials have mostly centered on amino acids which contain mixed-donor atoms and those containing dipeptide are rare.In this paper, a series of heteronuclear compounds was prepared through the reaction of the glycylglycine,2-hydrogen benzaldehyde and transition metal, alkaline earth metal or lanthanide metal and has been synthesized and characterized by elemental analysis, IR, TG, X-ray powder diffraction analysis, single single-crystal X-ray diffraction, ESR to explore the bonding of ligand and copper(II) or nickel(II) ion. The outline of paper is as follows:(1):A summarization of heterometallic coordination polymers and the research progress of coordination compounds based upon Schiff base ligands that related to our research and the purpose and significance of the subject.(2):We designed and synthesized metallo-ligand [CuL]-and obtained three heterometallic compounds in water-methanol built upon [CuL]-and metal salt: [Mn(CuL)2(H2O)4]-4H2O(l),[Zn(CuL)2(H2O)4]-4H2O(2),[Co(CuL)2(H2O)4]-4H2O(3). Three compounds are heterotrinuclear Cu(II)-M(II)-Cu(II)(M:Mn、Zn、Co) complexes. One tri-nuclear molecular unit ([(CuL)2M(H2O)4])(M:Mn.Zn、Co) linked with adjacent two units by intermolecular hydrogen bond, which formed an one dimensional ladder-like structure([(CuL)2M(H2O)4]n). The1-D ladders linked together by hydrogen bond through uncoordinated water molecule to form a2-D grid structure.[CuL]-in a2-D grid are inter digitated with those of neighboring2-D grids through hydrogen bond to form a3-D network.(3):We designed and synthesized metallo-ligand [CuL]-and obtained one heterotrinuclear Cu(II)-Mg(II)-Cu(II) complex [Mg(CuL)2(H2O)4]·4H2O(4) in water-methanol built upon [CuL]-and metal salt MgSO4. One tri-nuclear molecular unit ([(CuL)2Mg(H2O)4]) linked with adjacent two units by intermolecular hydrogen bond, which formed an one dimensional ladder-like structure([(CuL)2Mg(H2O)4]n). The1D ladders linked together by hydrogen bond through uncoordinated water molecule to form a2-D structure.(4):We designed and synthesized metallo-ligand [CuL]-and obtained three compounds in water-methanol built upon [CuL]-and metal salt:[Er(CuL)2(H2O)3(NO3)]H2O(5),[Sm(CuL)2(H2O)3(NO3)]H2O(6),[Gd(CuL)2(H2O)3(NO3)]H2O(7). Three compounds are heterotrinuclear Cu(Ⅱ)-M(Ⅲ)-Cu(Ⅱ)(M:Er、 Gd、Sm) complexes. One tri-nuclear molecular unit ([(CuL)2M(NO3)(H2O)3])(M:Er, Gd、Sm) linked with adjacent two units by hydrogen bond, which formed an one dimensional structure.(5):We designed and synthesized metallo-ligand [NiL]-and obtained two heterometallic compounds built upon [NiL]-and metal salt:[Zn(NiL)2(H2O)4]-8H2O(8),[Mn(NiL)2(H2O)4]·8H2O(9). Two compounds are heterotrinuclear Ni(Ⅱ)-M(Ⅱ)-Ni(Ⅱ)(M:Mn、Zn) complexes. One tri-nuclear molecular unit ([(NiL)2M(H2O)4])(M:Mn、Zn) linked with adjacent two units by intermolecular hydrogen bond, which formed an one dimensional ladder-like structure([(NiL)2M(H2O)4]n). The1D ladders linked together by hydrogen bond through uncoordinated water molecule to form a2-D grid structure.[NiL]-in a2-D grid are interdigitated with those of neighboring2-D grids hydrogen bond to form a3-D network.(6):Summary, conclusions and prospect.