The Type Of Decorated And Substituted Polyoxometalates: Synthesis, Crystal Structure And Properties

Polyoxometalates (POMs or Metal-Oxygen Clusters), are one kind of polynuclear complexes, which have definite structure, better thermal stabilities, redox activities, solubility and acid-base properties, etc., and many classic POMs is nano-size. POMs have been attracted intense interest and extensive research for their fascinating structures and potential applications, such as catalysis, photochemistry, porous materials, molecular magnetism, biology, and medicine.Seven POMs and a new mixed transition metal complex polymer have been synthesized by hydrothermal technique and/or aqueous synthesis, which via self-assemble and change the conditions of reaction. The compounds were characterized by single crystal X-ray diffractions, IR, XRD, TG, elemental analyses. The photoluminescence properties and photochromism properties of these compounds have been studied.[Cu(phen)2(HPW12O40)]·(phen) (1)(C6H6NO2)·(C5H6N)2·[PMo12O40]·(C6H5NO2)·2H2O(2)[Cu(en)2]2H2[{Cu(en)2}2(H2W12O42)]·6.5H2O (3)[Na6(H2O)14]H4[H2W12O42]·4H2O (4)[Cu(2,2-bpy)(Mo2O7)] (5)Cu2(phen)2(μ-O)2Mo(C4H3O5)2·7H2O(6)[Na(H2O)3]8H4[Mn4(H2O)2(GeW9O34)2]·13H2O (7)[Na(H2O)3]4H5[{Na(H2O)2}3{Mn(H2O)}3(SbW9O33)2]·11H2O(8)The compound 1 and 2 were based on the different POMs supramolecular compound:the helical formed via hydrogen-bond interactions between [Cu(phen)2]2+ cation and the free phen in compound 1, and extended into a three-dimensional supramolecular network; protonated isonic-isonic served as ID chains through hydrogen-bond interactions, and pyridine dissociated around polyoxometalate units in compound 2, which exhibited the attractive photochromism phenomena. Compound 3 represents ID chain based on polyoxoanion linked to two neighbors through four coordination groups ofμ2-[Cu(En)2]2+, and it extends into a three-dimensional supramolecular network by hydrogen bonding interactions. Compound 4 possess 2D structure through {Na3O12} linked to polyoxoanion. Compound 5 shows a ID chain constructed by Cu-bipy coordination modifying POMs. Compound 6 exhibits ID helical chain constructed by flexible ligand L-malic. Compound 7 and 8 are 3d-transition metal Mn substituted POMs, and show sandwich-type structures. Compound 7 exhibits a 2D layer by bridging Na+, and 8 shows a 3D opening network.