| In this paper, three types of aminopolycarboxylic acids,ethyleneglycol-bis-（2-aminoethylether）-N, N, N’, N’-tetraacetic acid （H4egta）,ethylenediamine-N, N, N’, N’’, N’’-pentaacetic acid （H5dtpa）, andtriethylenetetramine-N, N, N’, N’’, N’’’, N’’’-hexaacetic acid （H6ttha）, have beenselected as ligands, three rare earth metal ions, EuⅢ, HoⅢand ErⅢhave been chosenas cetral ions to synthesize seven novel complexes. We are particular investigated thestructure, spectroscopic properties and thermal stability of this seven complexes, theaim is get further information of structure and properties of Ln-APCA （APCA=aminopolycarboxylic acids） complexes. In addition, we choose the counter ion frominorganic salts to organic amine. It is important for us to study the interaction of rareearth metal complexes with proteide residues in the future.This paper is discussed as three parts according to the type of ligands.Part of H4egta, three novel complexes, namely,（mnH）2[EuⅢ（egta）]2·6H2O,（enH2）[HoⅢ（egta）（H2O）]2·6H2O and （enH2）[ErⅢ（egta）（H2O）]2·6H2O (mnH+isprotonated methylamine, enH22+is protonated ethylenediamine), have beensuccessfully synthesized. Results are as follows, EuⅢitself has fluorescence, thefluorescence of （mnH）2[EuⅢ（egta）]2·6H2O is markedly enhanced after coordinatingwith H4egta. According to the analysis of single crystal X-ray diffraction, thegeometry around the center EuⅢof （mnH）2[EuⅢ（egta）]2·6H2O adopts nine-coordinatepseudo-monocapped square antiprism, and it crystallize in the monoclinic crystalsystem with C2/c space group. Complex anions [EuⅢ（egta）]–connects to eath otherthrough carboxyl O atom of ligand forming a zigzag chain structure. Although（enH2）[HoⅢ（egta）（H2O）]2·6H2O and （enH2）[ErⅢ（egta）（H2O）]2·6H2O have differentrare earth metals, both of the center ion of them adopt nine-coordinatepseudo-monocapped square antiprism, and they crystallize in the monoclinic crystalsystem with P21/n space group. In addition, the ethylenediamine connect with four adjacent complex anions through hydrogen bonds in both of them, forming a2Dladder-like layer structure.Part of H5dtpa, two novel complexes, namely, Na4[EuⅢ（dtpa）（H2O）]2·11.5H2Oand （NH4）4[EuⅢ（dtpa）]2·10H2O, have been successfully synthesized. Results are asfollows, Fluorescence spectrum analysis display that both of them have fluorescentproperty. The single-crystal X-ray diffraction reveals thatNa4[EuⅢ（dtpa）（H2O）]2·11.5H2O have two independent nine-coordinate mononuclearstructural units [Eu（1）Ⅲ（dtpa）（H2O）]2–and [Eu（2）Ⅲ（dtpa）（H2O）]2–. The center EuⅢadopts pseudo tricapped trigonal prismatic conformation. It crystallizes in themonoclinic crystal system with P21/n space group.（NH4）4[EuⅢ（dtpa）]2·10H2O havetwo independent nine-coordinate binuclear structural units [EuⅢ（1）（dtpa）]24-and[EuⅢ（2）（dtpa）]24-. The center EuⅢadopts pseudo tricapped trigonal prismaticconformation. It crystallizes in the triclinic crystal system with Pī space group.Through hydrogen bonds, the crystal water and NH4+connect with adjacent complexanions, forming a2D planar structure.Part of H6ttha, two novel complexes, namely,（enH2）1.5[HoⅢ（ttha）]·4.5H2O and（enH2）1.5[ErⅢ（ttha）]·3H2O, have been successfully synthesized. Results are as follows,the X-ray crystal structure analysis reveals that both of them are nine-coordinatemononuclear structure, both of them have a free （non-coordinate） carboxyl groupanion, and they crystallize in the monoclinic crystal system with P2/n space group.However, they are obviously different in coordinate structure because they havedifferent the center metal. The center HoⅢof （enH2）1.5[HoⅢ（ttha）]·4.5H2O adoptpseudo tricapped trigonal prismatic conformation. The center ErⅢof（enH2）1.5[ErⅢ（ttha）]·3H2O is pseudo monocapped square antiprism. In addition, bothof them have two types of ethylenediamine, which form hydrogen bonds withadjacent complex anions, leading to the formation of a2D network and3D porestructure separately. |
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