Studies On Syntheses, Structures And Properties Of Rare Earth Complexes With N-sulfonyl-α-amino Acids

In this thesis,the studies of the Rare earth complexes of amino acids and transition metal complexes of N-sulfonyl-a-amino acids have been reviewed;the synthetical method of tolylsulfonyl chloride and N- p-tolysulfonyl amino acids have been improved;Nineteen new binary and ternary rare earth complexes of p-tolylsulfonyl-a-amino acids have been synthesized. Nine of them were studied by single crystal x-ray diffraction method. At the same time,some complexes were characterized by IR,TG-DTG,Fluorescence Spectrum and Elemental Analysis. The biological activity of some binary complexes was tested. By these ways,the structural features of the synthesized complexes have been studied systematically.The structure of Methyl-p-tolysulfonyl-glycine (TsGlyHMe 1) has been determined and it can be viewed as a mode of "V" form. Two molecules are joined to give a dimer by classical hydrogen bond,and the connection of the dimers via the unclassical hydrogen bond provides a 2-D network.The structures of Binary complexes of [Gd2(H2O)4(TsGlyH)6]n 2nH2O (2) ,[Er3(H20)6-(TsGlyH)9]n 5nH2O (3) and [La2(TsAlaH)6]n 4nH2O (4)(TsGlyH = N- p-tolysulfonylglycinate,TsAlaH = N- p-tolysulfonylalaninate) have been studied by single crystal x-ray diffraction method. All the complexes of 2,3 and 4 crystallize in triclinic system,space group Pi ,and have the structure of one dimensional poly-nuclear chain. In complex 2,the coordination number of Gd(III) is eight and the coordination geometry around Gd(III) is distorted square antiprism. The dimeric units of [Gd2(H2O)4 (TsGlyH)6 4H2O] are bridged by four bidentate bridging carboxylate groups between Gd(1) and Gd(2) to give a B'A'ABB"A" chain. In the complex 3,the coordination number of Er(III) and coordination geometry around Er(III) are same as complex 2. The difference between 2 and 3 is an unusual bidentate chelate carboxylate group in complex 3. The trimeric units of [Er3(H2O)6(TsGlyH)9] 5H2O is bridged by two bidentate carboxylate group between center atoms to form one dimensional polymeric chain. In complex (4),the coordination number of La(III) is nine and the coordination geometry is distorted tricapped trigonal prism. The coordination polyhedrons are linked by bridging bidentate carboxylate groups to form a polymeric chain. The distance between La(1) and La(1)# which are bridged by two bidentate bridging carboxylate and two tridentate bridging carboxylate is 0.41919nm,which is shorter than that of other complexes.The fluofescence spectra of Complexes of Ln-TsGlyH (Ln=La,Nd,Eu,Gd,Er,Yb) show that the fluorescence of ligand is quenched by Ln(III) ion. The results of the TG-DTGanalyses show that the Complexes of Ln-TsGlyH lost at first all the water molecule. As a second step they lost the -NHCH2COO- group at higher tempcrture,and then lost the -CH3 group on benzene ring. Finally they lost all phenylsulfonyl groups to become sulfalc of lanthanide. The complexes dissolve easily in water,and can hold effect of a nti bacteria even in low concentration,and that the effective antibacterial activity can be obtained by choosing different ligand or rare earth,indicates that this kind of complexes is a promising medicament worthy of further investigation.The structures of ternary complexes of [Eu2(H2O)2(phen)2(TsGlyH)6J(5),[Yb(H2O)2 (Phen)2(TsGlyH)2]Cl 2H2O(6),[Er2(H2O),(bpy)2(TsGlyH)6](7),[Yb2(I I2O)2(bpy)2 (TsGlyH)6](8),[Gd2(H2O)2(bpy)2(TsAlaH)6] (9),[Er2(II2O)2(bpy)2(TsAlaH)6](10). (phen -1,10-phcnanthroline,bpy - 2,2'-bipyridine) have been determined. The coordination number of the center metal ions in Complexes 5-10 is eight ,all the complexes crystallizes in the monoclinic system,space group P2|/n. Complex 6 is an unusual monomer;the molecular structure extends as a butterfly. Complexes of 5,7 8 9 and 10 are binuclear structure,their molecular structure and packing are similar to each olher. In the crystal the dimcric units pile up in the fashion of body-centered cubic. Four act as bidentate bridging ligand and two as unusual monodcntate ligands in six carboxylale group. The f...