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Synthesis And Antitumor Activity Of Inorganic-Organic Hybrids Substituted Based On Arsenotungstate

Posted on:2016-04-26Degree:MasterType:Thesis
Country:ChinaCandidate:J M LiuFull Text:PDF
GTID:2271330470461625Subject:Inorganic Chemistry
Abstract/Summary:PDF Full Text Request
POMs is an important research field in coordination chemistry, which have potential applications in catalysis, magnetic, optical, etc. Recent researches in the field of biomedicine have captured the attention of chemical and pharmaceutical researchers. By selecting the appropriate organic ligands modifying the polyoxometalates structure unit, we success to synthesis ten novel complexes by hydrothermal technique and aqueous solution. The chemical formulas of have been determined by elemental analyses and TG analysis: Na6[{Na(H2O)}3{Ni(Htaz)}3(As W9O33)2]·4H2O(1) Na6[{Na(H2O)}3{Co(Htaz)}3(As W9O33)2]·8H2O(2) Na6[{Na(H2O)0.5}3{Mn(Htaz)}3(As W9O33)2]·11H2O(3) [Ni(phen)3][Ni(OH)(phen)3][(As3W3O15)]·2H2O(4) [Co(phen)3][Co(OH)(phen)3][(As3W3O15)]·2H2O(5) [Cu(en)2(H2O)]2[{Cu(en)2}(As2W18O61)](6) [Ni(1,4-BDC)(4,4′-bpy)](7) [Ni(H2O)(1,4-BDC)(bpp)](8)(4,4′-bpy)[Zn(1,4-BDC)(2,2′-bpy)](9) [Zn(1,4-BDC)(bpp)](10)(taz = 1,2,4-1H-triazole, phen=1,10-phenanthroline, en=ethylenediamine, bpp=1,3’-di(4-pyridyl)propane, 4,4′-bpy =4,4’-bipyridine, 2,2′-bpy=2,2’-bipyridine, 1,4-BDC=1,4-benzenedicarboxylate)Ten compounds are structurally characterized by IR and single crystal X-ray diffractions. compounds 1-3 contain heterocaryosis sandwich-type [{Na(H2O)n}3{M(Htaz)}3(As W9O33)2]6-(n = 1 or 0.5) anions and sodium cations. In which taz, and water molecules to form {MO4(Htaz)} and {Na O4(H2O)m}(m = 1 or 2) segments, these fragments connect alternately in an edge-sharing mode forming a six-membered ring, the sandwich structures are formed 1D to 3D through hydrogen bonds and supramolecular. Compounds 4 and 5 are isomorphic. The asymmetric unit of 1 consists of [As3W3O15]3- polyanion and two outer floating {M(phen)3}2(M = Ni, Co). The [As3W3O15]3- polyanion contain nine bridging-oxygens, one tri-bridging oxygens and five terminal-oxygens. The structures are formed 1D to 3D through supramolecular interactions. Compound 6 is a typical Dawson structure, each two [As2W18O61]6-polyanion form a [(As2W18O61)2]12- dual-core tungstate clusters by an ordinary O atom and a [Cu(en)2]2+ anion. Every two units is formed 1D chain which infinite parallel to an axis via this connection, and almost in a horizontal plane, the formation of 2D and 3D structures via supramolecular interactions. Compounds 7-10 are synthesized by the transition metal and organic ligands, and the 1,4-BDC was acted as a tetradentate chelate bridging ligand. In compound 7, each transition metal ions are bridged by organic ligands to form 1D, 2D structures, and exhibite a 3D porous skeleton perfect cube. In this 3D structure, the 1,4-BDC as a linker, which diagonal distance is 14.778?×14.778?, the 4-4’-bpy as the linker, which diagonal distance is 15.207?×15.207?. In compound 8, the coordination environment of Ni II are both six-coordinated, the formation of 1D chain through organic ligands which the angular distance is 18.159?×15.396?, the formation of 2D layers and 3D networks through hydrogen bonding. The 2D layer of compound 8 is constructed via hydrogen bonding interactions. The compound 9 has two auxiliary ligands, one is external, and another set in the cavity of 1D chain, the 2D and 3D structure are formed through supramolecular and π...π stacking interactions. In compound 10, the 1D and 2D structures are formed by the organic ligands, which the angular distance is 16.006?×16.006?, the 3D porous structure is formed through hydrogen bonding interactions between O atom of the BDC and H atom of bpp ligand.The compounds 1-3 exhibit good electrocatalytic activity to reduce hydrogen peroxide and antiferromagnetic interactions between trinuclear M(II) clusters. In addition, compound 1 can be used as a potent inhibitor of He La cells. Analysis can be obtained from the fluorescence spectra of compounds 4-10, these compounds are generate deviation that compared to the corresponding free ligand, the result shows that the synthetic compounds can be used as luminescent materials. In addition, the photocatalytic studies of complexes 4-10 show that: with the increase of exposure time, the absorption peak of Rh B grows along with the reduced reaction time, and the degradation rate increase, it shows that these complexes can be used as a catalyst degradation of Rh B dye.
Keywords/Search Tags:Polyoxometalate, Electrochemical Propert, Antitumor Activity, Luminescence Property, Photocatalysis
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