| A series of novel organic-inorganic hybrid compounds with many kinds of polyoxometalates as basic building blocks have been systematically investigated by the modification, linkage and extension of different kinds of N-containing organic ligand in this paper. When we investigated the synthesis conditions and rules of these compouds, many factors such as the kinds of alkali, molar ratio of reactants and pH value influencing the structures of these compounds have also been studied. Then, 22 new POM-based organic-inorganic compounds have been assembled by altering the reaction conditions and reactant types under hydrothermal conditions. All these compounds have been structurally characterized by elemental analyses, IR, TG and X-ray single crystal diffractions. And partial compounds have also been investigated by XPRD, electrochemical and photocatalysis properties.1.Using （NH4）6Mo7O24, bix and bpp, Cu（OAc）2 as reactants, eight new Mo8-based compounds have been hydrothermal syntheszied and characterized by adjusting different structure directing agents （NaOH, en and TEA）. [Cuâ… ï¼ˆbix）][（Cuâ… bix）(δ-Mo8O26)0.5] （1） H（Cuâ… bix）[（Cuâ… bix）2(β-Mo8O26)]·2H2O （2） H3[Cuâ… ï¼ˆbix）2(β-Mo8O26)0.5](β-Mo8O26)0.5·2H2O （3） （H2bix）2(β-Mo8O26)0.5(β-Mo8O26)0.5·H2O （4） （H2bix）[（Hbix）2(γ-Mo8O26)]·2H2O （5） H2bix(γ-Mo8O26)0.5·H2O （6） [Cuâ… ï¼ˆbpp）][Cuâ… ï¼ˆbpp）(α-Mo8O26)0.5]·H2O （7） [（H2bpp）2(β-Mo8O26)] （8）Compounds 1 has a 3D （4,4）-connected framework with （64·82）（84·122） topology and compound 2 has a 3D （3,4）-connected framework with （62·81）2（62·82·102） topology. With the peneation of the copper-organic polymeric chains, 3D polythreaded frameworks were formed. Compound 3 has a 3D supramolecular network based upon (β-Mo8O26)4- anions and copper-organic units, with guest (β-Mo8O26)4- anions included. In compound 4, a 3D supramolecular arrangement is constructed by the hydrogen bond interactions between (β-Mo8O26)4- polyanions from different 2D structures and bix ligands. Compound 5 exhibits a unique bisupported structure built from Mo-N covalent bonds between (γ-Mo8O26)4- anions and bix ligands. This compound represents a rare example of organic-molecule-functionalized POM clusters that can be synthesized under hydrothermal conditions. In compound 6, a 3D supramolecular net is generated by hydrogen bonding interactions among water molecules, oxygen atoms of octamolybdate and nitrogen atoms of bix ligands. Compound 7 forms a 2D （3,4）-connected layer with （42·81）（61·84·101） topology. Compound 8 also has 3D supramolecular framework based on C-H…O hydrogen bonds between bpp and (β-Mo8O26)4- polyoxoanions.2.Using different metal ions, bix ligands, H3PO4 and Na2MoO4 as reactants, four new phosphomolybdate compounds have been prepared by altering molar ratio of H3PO4 and Na2MoO4 under certain pH value. CoH（bix）4[PMoVI8VV4O40（VIVO）2] （9） （H2bix）2（NaHP2Mo5O23）·2H2O （10） H2（bix）4[Cd（H2O）4][Cd（HPO4）4（H2PO4）4（MoO2）12（OH）6]?10H2O （11） （H2en）3（Co3P4Mo4O28） （12）Compound 9 consists of straight chains based on pseudo-keggin [PMoVI8VV4O40（VIVO）2]3- polyanions and [CoH（bix）4]3+ complex fragments, which are further connected into a three-dimensional （3D） open framework by hydrogen bonding interactions between polyanions and organic ligands bix. Compound 10 shows 3D supramolecular networks constructed from weak interactions among free biprotonated bix, water and oxygen atoms of polyanions [P2Mo5O23]6-. In compound 11, [Cd（HPO4）4（H2PO4）4（MoO2）12（OH）6]4- polyanions are linked by [Cd（H2O）4]2+ cations to build one-dimensional （1D） chains. Then weak interactions among free bix ligands, water and oxygen atoms of the polyanions extend these 1D chains to 3D supramolecular frameworks. Compound 12 exhibits open-framework structures. Interestingly, it also shows 1D left and right-handed helical chains and 2D （6,3）-layers.3.Using different POM units as catalysis agents, flexible ligand bpp, metal ions and three kinds of frameworks with tetradentate in-situ ligands have been prepared by adjusting different pH value. Cuâ… 3（L1）2（L2）[PMoVI8VV4O40（VIVO）2]?2H2O （13） [Cuâ… 2Cl2（L3）] （14） [Zn3（BTC）2（chtpy）（H2O）2]·2H2O （15）Compound 13 exhibits unique 3D MOFs with two topologies （42·84）（42·83·101）（86）2 and （43·83）（42·84）（44·62·89）（410·61·83） due to different definitions of nodes. It represents the first example that dehydrogenative coupling has been employed to yield a novel tetradentate coplanar dye molecule in POM-based MOFs. Compound 14 shows a two-fold diagonal/diagonal inclined interpenetration. Compound 15 exhibits an unprecedented （3,4）-connected （82·10）2（83）2（84·10·12）（85·10） topology which has been reported for the first time and shows self-penetrating nature at the same time.4.Using CuBr, chelate ligand dafo and different POM building units, three kinds of compouds have been assembled and characterized under hydrothermal conditions. H[Cuâ… ï¼ˆdafo）2]3{[Cuâ… ï¼ˆdafo）2]2P2W18O62}·H2O （16） [Cuâ… ï¼ˆdafo）2]3PMo12O40 （17） [Cuâ… ï¼ˆdafo）2]4SiW12O40 （18）Compound 16 exhibits 3D supramolecular framework. With the aid ofÏ€-Ï€stacking and hydrogen bonding interactions, 1D supramolecular cavity accommodating POMs anions is generated in compound 17. Compound 18 has similar fundamental units with 17, but it didn’t fabricate porous structures for the incorporation of different POMs. 5.Using different metal ions, rigid ligand 4,4’-bipy and different POM building units, two new organic-inorganic hybrid compounds with one kind of ligand have been prepared. [Ag（4,4’-bipy）]4（H2P2Mo5）·3H2O （19）[4,4’-H2bipy]3[SiMnW11O39]·1.25H2O （20）Compound 19 contains unique 3D metal organic frameworks based on silver-complex fragments and hexa-connected P2Mo5 clusters via covalent bonds and represents the highest connection numbers of P2Mo5 clusters to date. Compound 20 represents the first characterized compound containing 1D zigzag chain of transition metal substituted Keggin heteropolytungstate, which is connected through a common oxygen atom.6.Using different metal ions, chelate ligand dafo and rigid ligand 4,4’-bipy and keggin-type POM building units, two new organic-inorganic hybrid polyoxotungstates with mixed ligands have been prepared. [Ag（dafo）2]2{[Ag（4,4’-bipy）]2SiW12O40} （21） [Cd2（dafo）4（4,4’-bipy）（H2O）2]（dafo）SiW12O40 （22）Compound 21 exhibits a new 3D framework, the supramolecular interaction stable the whole structure. In compound 22, the 1D hybrid chain extended to unique the 3D structure via weak CH···O interaction. To our best knowledge, it is the first time that saturated Keggin-type polyoxotungstates interact with dafo and 4,4’-bipy at the same time. bpp = 1,3-bis（4-pyridyl）propane bix = 1,4-bis（imidazole-1-ylmethyl）benzene, dafo = 4, 5-diazafluoren-9-one 4,4’-bipy = 4,4’-bipyridine phen = 1,10-phenanthroline en=1,2-ethylenediamine L1=a,a-1,4-dihydroxy-e,e,e,e-1,2,4,5-tetra（4-pyridyl）cyclohexane L2=1,2,4,5-tetra（4-pyridyl）-benzene L3=a-1-hydroxy-e,e,e,e-1,2,4,5-tetra（4-pyridyl）cyclohexane... |
