Build A New Type Of Organic-Inorganic Hybrid Compounds Based On Polvoxometalates And Nitrogen Ligands

In this paper, a systematic study multiple types of polyoxometalate （polyoxometalate） asthe basic building units, the use of different types of nitrogen-containing organic ligandsmodification, bridging and build a series of novel structures and potential applications thevalue of multi-dimensional organic-inorganic hybrid compounds. In this paper, the use ofpolyoxometalates as the precursor, different transition metalions and rigid （flexible） nitrogenligands as building blocks,14kinds of unreported polyoxometalate-based organic-inorganichybrid compounds were designed and synthesized. They are characterized by elementalanalysis, IR, TG and single crystal X-ray diffraction analysis and some of them werepreliminary studied on photocatalytic properties and electrochemical properties. The majorresults are as follows:1、The use of Keggin/pseudo-Keggin POMs as the precursor, the organic ligand bix andtransition metal ions （Mn, Zn and Cu） were employed to synthesize four new POM-basedMOFs:[HMnII（bix）₄][PMo^VI8VV4O₄₀（^VIVO）₂]2H₂O1)[Zn（bix）₄][PMo^VI9VV3O₄₀（^VIVO）₂]2H₂O （2）[Cu（bix）₄][PMo^VI9VV3O₄₀（^VIVO）₂]4H₂O （3）[Cu^I（bix）]₂[Cu^I（bix）]（bix）[PMo₁₂O₄₀]4H₂O （4）Compound1consists of an infinite1D chain constructed from [HMnII（bix）₄]³⁺cationsand the reduced bi-capped pseudo-Keggin polyoxoanions [PMo^VI8VV4O₄₀（^VIVO）2]3-. Withthe aided hydrogen bonds, these1D chains extend to3D supramolecular frameworks.Compounds2and3are isostructural and consist of the bi-supporting Keggin polyoxoanions[PMo^VI9VV3O₄₀（^VIVO）2]2-and [M（bix）₄]2+（M=Zn, Cu） coordination polymer fragments,resulting in the3D supramolecular frameworks via weak interactions. Compound4iscomposed of the1D ladder-like chains [Cu（bix）]nn+, which are filled in the3Dsupramolecular cavities and stabilize the whole framework structures via the hydrogen bonds.In addition, the electrochemical properties and photocatalytic properties of compounds1-4have also been investigated.2、In this paper, we choose [α-SiW₁₂O₄₀]4-,[α-SiW9O34]10-and [BW₁₂O₄₀]5-polyoxoanionsas inorganic building blocks to synthesize four new organic-inorganic hybridcompounds：[Cu5I（4,4’-bpy）3（2,2’-bpy）₄][BW₁₂O₄₀]·H₂O（5）,[Ni_0.5（2,2’-bpy）_1.25][Ni（2,2’-bpy）₃][Ni（2,2’-bpy）₂（H₂O）(SiW^VI11WVO₄₀)]·0.5H₂O （6）,[H₂bpy]₂[Zn（2,2’-bpy）₃]₂[Si₂W₁₈O₆₂]·1.5H₂O （7） [CuII（2,2’-bpy）₂]₂[SiW₁₂O₄₀]·2H₂O （8）.Compound5is a novel [BW₁₂O₄₀]5-polyoxoanion bisupported by copper（I） coordinationcations with mixed2,2’-bpy and4,4’-bpy ligands. The compound6[SiW^VI11W^V40]5-anionas monodentate ligands, covalent connection of [Ni（2,2’-bpy）2]2+. Compound7is composedof a novel [Si2W18O62]8-cluster and [Zn（2,2’-bpy）3]2+complexes, which held together into a3-D （three-dimensional） supramolecular network through hydrogen-bonding andπ-πinteractions. Compound8of copper by [SiW₁₂O₄₀]4-double support transition metalcomplexes unit.3、With multi-molybdate anions transition metal organic amine-modified organic-inorganichybrid compounds：Cu₅^IBBTZ₃H₂O[β-MoVMo₇^VIO₂₆]（9）[Zn（2，2’-bipy）₂]₂[Mo₄^VIMo2^VO19][4，4’-bipy]（10）[Cu^I（bpp）][Cu^I（bpp）(α-Mo₈O₂₆)_0.5]·H₂O （11）Compound9is the first case to restore the state with molybdate [β-MoVMo^VI7O26]3Dinterpenetrating network compounds, compound10is rarely reported to [Mo4^VIMo2^V19]double support of the transition metal complex fragment;compounds,11transition metalcomplexes material fragments [α-Mo₈O₂₆]4-anion formation of one-dimensional ladder-likechain, and each of [Cu1（bpp1）]22+cationic fragment and twoadjacent [α-Mo₈O₂₆]4-Theterminal oxygen connected to build a two-dimensional layer structure. The compounds can beseen as with （42·81）（61·84·101） topology （3,4）-connected layers.4、U sing molybdenum acid and nitrogen ligands under the conditions of the hydrothermalsynthesis of three new organic-inorganic hybrid compound:[H₂（bpp）₂][Mo₈O₂₆]（12）[H₂（bbi）]₂[PV₂MoMo^VI11O44]（13）[H₂（bix）]₂[PMo₁₂O₄₀]·2H₂O （14）Compound12with the acid anion clusters (β-Mo₈O₂₆)4-through the terminal oxygen ofpoly connected into one-dimensional chain structure. Supramolecular structure throughhydrogen bonding. Compound13, the Keggin anion [PV2Mo^VMo^VI11O44] opposite ends ofthe buckle through the four bridging oxygen atoms of two tetravalent V cap. Constitute asupramolecular compounds through hydrogen bonds. Compound14is a typical Keggin typeheteropoly anion and protonated bix ligands constitute a supramolecular role of hydrogenbonds weak.