Syntheses And Properties Of Hybrid Inorganic-organic Compounds Constructed From Bis(triazole) Ligands And Polyoxomolybdates

In this work, we focus on building a series of novel inorganic-organic hybrids by usingdifferent bis（triazole） ligands and several kinds of polyoxomolybdates. The syntheticconditions and rules have been investigated. The experimental results will provide a referencefor the controlled synthesis of hybrid inorganic-organic polyoxomolybdate compounds.Nineteen new hybrid inorganic-organic polyoxomolybdate compounds have beensynthesized by adjusting temperature, pH value, and staring materials under hydrothermaltechnique. They have also been structurally characterized by elemental analyses, IR, PXRD,and single crystal X-ray diffractions. Additionally, the TGA, electrochemical, andphotocatalytic properties of some compounds have been investigated.1. A new polyanion (Mo₁₂O₃₉)^6-has been obtained. Three hybrid inorganic-organiccompounds have been synthesized by using L1ligand and (Mo₈O₂₆)^4-polyanion.[{Cu^II₃（L1）₄（H₂O）₂}{Mo₁₂O₃₉}]₀.5·3H₂O （1）[Zn2（L1）2（H₂O）4]0.5[(γ-Mo₈O₂₆)（L1）2]0.5·4H₂O （2）[Co2（L1）5(γ-Mo₈O₂₆)]_0.5·2.5H₂O （3）[Ni2（L1）5(γ-Mo₈O₂₆)]_0.5·2.5H₂O （4）L1=1,2-bis（1,2,4-triazol-1-yl）ethaneThese four compounds were synthesized under similar conditions except for utilizingdifferent transition metal cations. Compounds1and2are2D structure constructed from(Mo₁₂O₃₉)^6-and (Mo₈O₂₆)^4-polyanions, respectively. Compounds3and4are isostructural,exhibit interesting3D framework build by (Mo₈O₂₆)^4-polyanion.2. Five hybrid inorganic-organic compounds have been synthesized by using[（As3O3）2（ZnO6）Mo₆O₁₈]4-polyanion and different bis（triazole） ligands.[ZnL1（H₂O）3{（As₃O₃）₂（ZnO₆）Mo₆O₁₈}₀.5]·4H₂O （5）[Zn（L2）2][（As3O3）2（ZnO6）Mo₆O₁₈]0.5·2H₂O （6）[Zn（L3）（H₂O）₄]_0.5[Zn（L3）₂{（As₃O₃）₂（ZnO₆）Mo₆O₁₈}]_0.5·4H₂O （7）[Zn2（L4）₃（H₂O）₃{（As₃O₃）₂（ZnO₆）Mo₆O₁₈}]·4H₂O （8）[Zn（₀.5）（L5）（H₂O）][Zn（₀.5）（L5）{（As₃O₃）₂（ZnO₆）Mo₆O₁₈}_0.5]·H₂O （9）L2=1,3-bis（1,2,4-triazol-1-yl）propaneL3=1,4-bis（1,2,4-triazol-1-yl）butaneL4=1,5-bis（1,2,4-triazol-1-yl）pentaneL5=2,2’-bis（1,2,4-triazol-l-yl）etherWith the increase of ligand length, compounds5-8show1D and2D structures,respectively. Compound9possesses a3D polythreading structure feature. This may be due tothe ether chain more flexible than alkyl chain.3. Ten interesting hybrid inorganic-organic compounds have been synthesized by utilizing [Mo₆O₁₈（O₃AsPh）₂]4-or [（PhAsO₃）₄Mo₁₂O₃₄]^4-building blocks and differentbis（triazole） ligands.[Cu^I4（L1）₄（H₂O）₄][（PhAsO₃）₄Mo₁₂O₃₄]2H₂O （10）[Cu₈（L2）₈{（PhAsO₃）₄Mo₁₂O₃₄})₂]·H₂O （11）[Cu（L4）（HL4）₂{（PhAsO₃）₄Mo₁₂O₃₄}]·2H₂O （12）[Cu^I2（L1）₂][Cu^I2（L1）2Mo₆O₁₈（O₃AsPh）₂]（13）[Cu^I4（L3）₄Mo₆O₁₈（O₃AsPh）₂]（14）[Cu^I4（L4）₄Mo₆O₁₈（O₃AsPh）₂]（15）[Cu^I4（L6）₂Mo₆O₁₈（O₃AsPh）₂]（16）[Cu₂（L1）₄Mo₆O₁₈（O₃AsPh）₂]_0.5·2H₂O （17）[Cu₂（L2）₄Mo₆O₁₈（O₃AsPh）₂]（18）[Cu₂（L7）₄Mo₆O₁₈（O₃AsPh）₂]（19）L6=1,6-bis（1,2,4-triazol-1-yl）hexaneL7=1,4-bis（1,2,4-triazol-1-ylmethyl）benzeneCompounds10-19were obtained in different pH values （for10-12, pH≈2; for13-19,pH≈3-5）. Compound10is an isolated structure. Compound11belongs to the8-connected3D structure. It exhibits photocatalytic activity for dye degradation under visible light.Compound12shows a diamond-type network. Compound13is an unusual3Dpolypseudo-rotaxane architecture framework. Compound14presents a3D self-penetratedstructure. Compound15is a rare example of a2D→3D polycatenated POMOFs with helixchain motif. Compound16reveals a3D interlaced teteranodal （3,4,6）-connected network.Compound17exhibits3D open framework. Compound18shows a complicated3D structure.Compound19also reveals3D open framework.