| In this paper, sixteen tungstophosphates with wheel-type, boat-like and sandwich-type based on hexavacant Dawson structure ({P2W12}) and trivacant Keggin structure({SbW9}) have been obtained in aqueous solution by routine synthetic method. In these heteropoly anions, the transition metal ions of Co(II),Ni(II),Zn(II) and estertin groups have been introduced into the skeletons of these polyoxoanions. We firstly foundγ-{P2W12} subunit in the syntheses and firstly obtained eight single-crystals of polyoxometalate-based estertin derivatives. These compounds have been characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, TG analysis, electrochemical analysis and NMR. Their electrocatalytic properties toward the reduction of hydrogen peroxide have been investigated by cyclic voltammetry (CV), and Anti-tumor activity of 14 in vitro has been initially studied by the MTT method with three cancer cell lines of Hela, U87 and HT1080 .1. The 3d-transition-metal-modified tetrameric wheel-type polyanions {P8W48+n} based on {P2W12} subunit have been synthesized by introducing 3d transition metals (CoII, NiII, ZnII) and WVI to the hexavacant Dawson structures, including six new {P8W48+n} clusters as follows: K4Na22[{Co(H2O)2Cl}{Co(H2O)3}2{Co(H2O)5}1.5{Co(H2O)3}{H4P8W49O187(H2O)}]- 2NaCl?41.5H2O (1) K14Na14[{Co(H2O)3}2{{Co(H2O)4}2{H4P8W49.5O188.5(H2O)1.5}]?47H2O )2) Na30[{Ni(H2O)3}2{Ni(H2O)3}1.5{H3P8W49O187(H2O)}]·41.5H2O (3) K4Na50 [{Zn2(H2O)2}2{Zn2(H2O)7}(α,γ,α,γ-H2P8W48O184)][{Zn4(H2O)9}{α,α,α,α- H4P8W48O184}]·83H2O (4) K12Na45[{Zn2(H2O)9}0.75{Zn2(H2O)5}{Zn2(H2O)2}{α,γ,α,γ-P8W48O184}]- [{Zn2(H2O)7}{Zn2(H2O)2}2{α,γ,α,γ-P8W48O184}]·94H2O (5) Na35[{Zn(H2O)4}2.5{α,α,α,α-P8W48O184}]·48H2O (6)2. Three new multi(organotin)-decorated wheel-type {P8W48} polyoxometalates have been obtained by the reaction of {P2W12} subunit and estertin precursors in acetate buffer solution led to the hydrolysis of estertin into carboxyethyltin group: K5Na30 [{Sn(CH2CHCH3COO)(H2O)2}2{HP8W48O184}]·53.5H2O (7) K4Na)26){[Sn(CH2CH2COO)(H2O)2]5[P8W48O184]}·48H2O (8) K3Na25[{(Sn CH2CH2COO)3(H2O)4}2{P8W48O184}]·120H2O (9)3. A new multi(organotin) and CoII-decorated wheel-type {P8W48} polyoxometalate cluster has been synthesized based on {P2W12} subunit and estertin precursor, and meanwhile the 3d transition metal CoII indroduced: KNa20[({Co(H2O)4}0.5{Co(H2O)3Co(H2O)6(SnCH2CH2COO)1.25SnCH2CH2COO(H2- O)})2{P8W48O184}]·96H2O (10)4. Two new tetra(carboxyethyltin)-decorated boat-like polyoxometalate clusters have been successfully obtained by assembling of two kinds of estertin precursors and hexavacant Dawson-typeα-[P2W12O48]14-: Na16[K2Na2{Sn(CH2)2COO}4(H2O)2{WO5(H2O)}(P2W15O56)2]?37H2O (11) Na16[K2Na2{Sn(CH2CHCH3COO)}4(H2O)2{WO5(H2O)}(P2W15O56)2]·12H2O (12)5. Four new estertin derivatives based on trivacant Keggin-type [β-SbW9O33]9- cluster with sandwich-type structural feature, and the single crystals of compounds 14 and 15 have been determined: Na4K6[{Sn(C3H4O2)}2(WO2)2(B-β-SbW9O33)2]·7H2O (13) Na6K4[{Sn(C3H4O2)}2{Sn(C3H4O2)(H2O)}2(B-β-SbW9O33)2]·14H2O (14) Na4K6[{Sn(C4H6O2)(H2O)}2(WO2)2(B-β-SbW9O33)2]·19H2O (15) Na6K4[{Sn(C4H6O2)}2{Sn(C4H6O2)(H2O)}2(B-β-SbW9O33)2]·8H2O (16)... |
