Designed Assembly, Structural Characterization And Properties Of Transition-metal-Lanthanide Heterometallic Arsenotungstate Derivatives

In this dissertation, we have explored the system containing K14[As2W19O67(H2O)], FeCl3·6H2O, CuCl2·2H2O, lanthanide cations and aminoacids. In this reaction system, there are some difficulties to be faced by us:(1) the solubility of these reaction components is small in the same reaction medium; (2) there is the unavoidable competitive reaction among transition-metal (TM) cations, lanthanide (Ln) cations and K14[As2W19O67(H2O)]. By controlling the reaction temperature, the reaction time, the pH of solution and the molar stoichiometry of reactants, we have successfully obtained two series of purely inorganic TM-Ln heterometallic arsenotungastate derivatives and one class of organic-inorganic hybrid TM-Ln heterometallic arsenotungastates derivatives with amnioacid components, which have been charactered by IR spectra and X-ray sing-crystal diffraction. Their thermogravimetric (TG) analyses, solid state photoluminescence (PL) and antimicrobial activity have been invstigated.The dissertation can be divided into three sections to introduce my work during the master study:Section 1:Six novel inorganic CuⅡ-LnⅢ heterometallic arsenotungastates K1.5La1.5[La(H2O)8]2 [Cu3(H2O)3][B-α-AsW9O33]2·24H2O (1), Na3K4[Y(H2O)7][As2W19Cu2O67(H2O)3]·21 H2O (2), Na3K4[Pr(H2O)8] [As2W19Cu2O67(H2O)3]·21H2O (3), Na2K3.5Nd0.5[Nd(H2O)8][As2W19Cu2O67(H2O)3]·22H20 (4), Na2K3.5Sm0.5 [Sm(H2O)8][As2W19Cu2O67(H2O)3]·22H2O (5) and Na2K3.5Eu0.5[Eu(H2O)7][As2W19Cu2O67(H2O)3]-22H2O (6) have been prepared in the conventional aqueous solution. The anticancer activity measurements indicate that 5 and 6 show good inhibitory for HCT-116 and HepG2.Section 2:Four inorganic FeⅢ-LnⅢ heterometallic arsenotungastates based on trivacant Keggin [B-β-AsW9O33]9- fragments KNa2{La(H2O)7[Fe4(H2O)10(B-β-AsW9O33)2]}·21H2O (7), KNa2{Pr(H2O)7 [Fe4(H2O)10(B-β-AsW9O33)2]}·21H2O (8), KNa2{Nd(H2O)7[Fe4(H2O)10(B-β-AsW9O33)2]}·21H2O (9) and KNa2{Sm(H2O)7[Fe4(H2O)10(B-β-AsW9O33)2]}·21H20 (10) have been isolated under hydrothermal conditions.7-10 display the rare inorganic 2-D extended structures constructed from tetra-FeⅢ sandwiched [Fe4(H2O)10(B-β-AsW9O33)2]6- units Ln3+ cations. Moreover, their thermogravimetric properties have been investigated.Section 3:Nine isostructural organic-inorganic hybrid FeⅢ-LnⅢ heterometallic arsenotungastates with aminoacid ligands [La(H2O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9O33]·2-20 H2O (11), [Pr(H2 O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (12), [Nd(H2O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9 O33]2·20H2O (13), [Sm(H2O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (14), [Eu(H2O)8]2[Fe4 (H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (15), [Gd(H2O)8]2 [Fe4(H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (16), [Tb(H2O)9]2[Fe4(H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (17), [Dy(H2O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9 O33]2·20H2O (18) and [Er(H2O)8]2[Fe4(H2O)8(L-thr)2][B-β-AsW9O33]2·20H2O (19) have been made under hydrothermal conditions. Their common features are that they are discrete structures based on a tetra-iron substituted sandwich-type unit [Fe4(H2O)8(L-thr)2(B-β-AsW9O33)2]6- with two pendant [Ln(H2O)g]3+ cations. Furthermore, solid state photoluminescence of 15 and 17 have been measured at room temperature and they all display the characteristic emission of the Lnm ions.