| The paper aims at exploring to synthesize novel trans-metal substituted tungstate-oxo clusters.The experiments is derected by the idea of lacunary directed synthesis under hydrothermal condition.According to the literature,we prepared lacunary tungstate-oxo clusters as precursors,such as Na9[A-?-PW9O34]·7H2O,Na10[A-?-SiW9O34]·24H2O and so on.At the same time,Ni?Cu?Zr were regarded as the primary researched object.With the help of organic ligand,we expect to introduce the metal ions to gather on the vacant sites to form high-nuclear metal substituted tungstate-oxo clusters or aggregates.Under the aboved condition,we successfully synthesized six new trans-metal substituted tungstate-oxo clusters,which are characterized and analyzied by PXRD?IR?TG.The formulas of these compounds are as follows:H10{[Ni?H2O?5]2[Ni4?en?2(PW9O34)2]}{[Ni?en??dap?][Ni?dap?2]2[Ni4?en?2(PW9O34)2]}?9H2O[en=ethylenediamine]?3-1?H4[Ni6?OH?3?en?3?py?4(PW9O34)]?3H2O?3-2?{[Cu?2,2-bpy??H2O?]2[Cu?2,2-bpy??H2O?2]Cl}[Cu?2,2-bpy?][SiW11.25Cu0.75O40]?H2O?3-3?[?py?1.5][Cu?enMe?][Cu?enMe?2?H2O?]2[Cu?py?(PW11O39)]?2H2O?3-4?H3[Cu?en??enMe??H2O?][Cu?en?2][Cu?py?2?enMe?][Cu?py?(SiW11O39)]?H2O?3-5?Na6H5[Zr4?OH?2?H2O??CH3COO??OCH2COO?2(GeW10O37)2]·21H2O?3-6?K2Na10[Zr8??2-OH2?6?GeO4?6(H7GeW10O38)4]?43H2O?3-7?Compound 3-1 is a novel 2-D inorganic-organic hybrid sandwich-type tera-NiIII polyoxotungstate coodinated by mixed organoamines.Compound 3-2 is a[Ni6PW9]clusters with py and en.Compound 3-3 is a Cu substituted tungstate-oxo clusters,which is noticed is that there is hanging a Cu cations cluster that contains three Cu cations connected by a Cl.The same to 3-3,compound 3-4 is a 0D Cu substituted tungstate-oxo clusters.While,compound 3-5 is synthesized on the basis of 3-4 and there is Cu cations cluster decorated with enMe and py.Compound 3-6 is a sandwich-type tera-Zr polyoxotungstate coordinated by CH3COOH and CH2OCOOH.Compound 3-7 is a octa-Zr polyoxotungstate decorated with GeO4,which is seldom reported. |
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