| In this paper,bis-pyridyl-bis-amide,2-pyridyl-pyrazinamide and 4-pyridino-bistriazol are selected as the major ligands to react with A-series/B-series Anderson-type polyoxometalates(POMs)/polyoxovanadates/octamolybdates and transition metal ions under hydrothermal conditions.Twenty-nine POMs-based metal organic complexes have been synthesized,which are structurally characterized by IR,TG,powder X-ray diffraction and single crystal X-ray diffractions.The electrochemical properties and photocatalytic properties towards methylene blue(MB),rhodamine B(RhB)and congo red(CR)of these complexes have been studied as well.1.The classical A-series Anderson-type[TeMo6O24]6-anions were used as inorganic building units to assemble with Cu?,Zn?,Co?,and Mn? ions and flexible bis-byridyl-bis-amide ligands with different spacer lengh and Npy substitution patterns(3-dpye= N,N'-bis(3-pyridinecarboxamide)-1,2-ethane,4-dpye= N,N'-bis(4-pyridinecarboxamide)-1,2-ethane,3-dpyp=N,N'-bis(3-pyridinecarboxamide)-1.3-propane,4-dpyp=N,N'-bis(4-pyridinecarboxamide)-1.3-propane,3-dpyb=N,N'-bis(3-pyridinecarboxamide)-1,4-butane,4-dpyb=N,N'-bis(4-pyridinecarboxamide)-1,4-butane,4-dpyh=N,N'-bis(4-pyridinecarboxamide)-1,6-hexane)under hydrothermal conditions,resulting in twelve novel POM-based metal-organic complexes.[Mn2(3-H2dpye)(TeMo6O24)(H2O)6]·4H2O(1)[Cu4(?3-OH)2(H2O)6(4-dpye)2(TeMo6O24)]· 2H2O(2)[Cu2(4-Hdpye)2(TeMo6O24)(H2O)6]·4H2O(3)H2[Zn4(3-Hdpyp)2(TeMo6O24)2(H2O)16]·6H2O(4)[Cu2(4-Hdpyp)2(TeMo6O24)(H2O)6]·4H2O(5)[Cu3(3-dpyb)2(TeMo6O24)(H2O)8]·4H2O(6)[Zn3(3-dpyb)2(TeMo6O24)(H2O)12]·8H2O(7)[Co2(H2O)6(TeMo6O24)](3-H2dpyb)-2H2O(8)[Cu2(4-Hdpyb)2(TeMo6O24)(H2O)6]·4H2O(9)[Zn2(4-Hdpyb)2(H2O)6(TeMo6O24)]· 6H2O(10)[Co2(4-Hdpyb)2(H2O)6(TeMo6O24)]· 6H2O(11)[Cu4(?2-OH)(?3-OH)(H2O)6(4-dpyh)(TeMo6O24)]·H2O(12)Complex 1 is a two-dimensional(2D)layer,which is constructed from A-series Anderson-type[TeMo6024]6-(TeMo6)anion,flexible bis-pyridyl-bis-amide 3-dpye and Mn? ion.Complex 2 shows a 2D metal-organic layer based on[Cu4-TeMo6]2+ inorganic chain.Complexes 3 and 9 are isostructural,based on 0D discrete units with different spacer lengh.Complex 4 displays a discrete structure constructed from TeMo6 and Zn? ion.Complex 5 shows a Cu-TeMo6 inorganic layer with the organic ligand consolidating the structure.Complex 6 is a 3D cage-like framework constructed from the TeMo6 polyoxoanions.Complex 7 displays a 1D wave-like chain.Complex 8 is a 1D chain constructed from the metal center and polyoxoanion.Complexes 10 and 11 represent isostructural,consisting of 0D discrete units.Complex 12 shows a 3D metal-organic framework constructed from metal ions,ligands and Anderson-type TeMo6.The different spacer length,Npy substitution patterns,metal ions and the pH value of reaction show great effect on the final structures.Complex 1 exhibits good electrocatalytic activities for the reduction of BrO3-and H2O2.Complexes 1-12 show remarkable photocatalytic activities for the degradation of MB and RhB under UV light irradiation.2.By using B-series Anderson-type POM to react with three pyridyl derivatives ligands and Cu?/Mn? ions under hydrothermal conditions,eleven POM-based metal-organic complexes have been synthesized.[Cu2(2-pdya)(CrMo6(OH)5O19)(H2O)2]·3H2O(13)[Mn2(4-pdtz)2[CrMo6(OH)5019](H2O)4](14)[Cu(3-dpye)0.5(?-Mo8O26)0.5(H2O)4]·H2O(15){Mn(3-dpye)0.5[CrMo6(OH)6O18](H2O)} ·(3-H2dpye)0.5(16)[Cu(4-Hdpyp)2(?-Mo8O26)(H2O)2]·4H2O(17)H[Cu2(3-dpyb)2(C2O4)(CrMo6(OH)6O18)]·8H2O(18)[Cu(4-dpyb)(CrMo6(OH)6O18)2(H2O)2][Cu(4-dpyb)(H2O)4](4-H2dpyb)·6 H2O(19)[Cu4(?-OH)2(H2O)4(3-dpyh)(?-Mo8O27)]·4H2O(20)[Cu2(4-dpyh)(CrMo6(OH)5O19)(H2O)8]·10H2O(21)Cu5(?2-OH)2(4-dpye)2[(CrMo6(OH)5O19)]2(H2O)10(22){Cu(4-Hdpye)[CrMo6(OH)6018](H2O)2}·2H2O(23)[2-pdya= 2-pyridyl-pyrazinamide,4-pdtz= 4-pyridino-bistriazol]Complex 13 is a 1D inorganic chain formed by B-type Anderson-type CrMo6 and Cu ions,in which 2-pdya offers four coordination sites to consolidate the 1D structure.Complex 14 represents the first example of 1D structure consisting of Anderson-type POM and 4-pdtz.Complex 15 shows a 2D layer based on 1D infinite[?-Mo8O26]n4n-chain.Complex 16 is the first 3D metal-organic framework,in which Anderson-type POMs combine with Mn ions.Complex 17 exhibits a 1D fishibone-like chain.Complex 18 shows a 1D ring-like chain structure.Complex 19 contains two types of 1D chains.Complex 20 is a metal-organic framework formed by the 2D[Cu4(?3-OH)2(H2O)4(?-Mo8O27)]layer.Complex 21 is 0D discrete structure constructed from[Cu2(4-dpyh)]4+ and CrMo6.Complexes 22 and 23 share the same experimental materials but different pH value,showing 3D metal-organic framework and 2D inorganic layer,respectively.The structures of these complexes are influenced by the various coordination modes of the ligands and POMs.Complex 13 shows good electrocatalytic properties in the reduction process of H2O2 and bromate.Complexes 13-23 show high photocatalytic activity toward the degradation of MB,RhB and CR under UV irradiation.In addition,complex 23 shows not only photocatalytic activity but also physical adsorption towards the organic dyes.3.By employing the octamolybdates and polyoxovanadates as inorganic building blocks,Zn ion as metal center,flexible bis-pyridyl-bis-amide with different spacer lengh as organic ligands,six POM-based metal-organic complexes were synthesized under hydrothermal conditions.(3-H2dpye)(?-Mo8O26)0.5(24)(4-H2dpye)[(4-dpye)(?-Mo8O26)]0.5·2H2O(25)[(3-H2dpyp)2(?-Mo8O26)]· 2H2O(26)[(4-H2dpyp)2(?-Mo8O26)]· 2H2O(27)[V2O6Zn(4-dpye)]n(28){[Zn(3-Hdpye)(H2O)5]2[V10O28]} · 4H2O(29)Complex 24 is a 3D supramolecular structure composed of 1D ?-Mo8O26 chain and 3-H2dpye ligands.Complex 25 is constructed from 1D chain containing Mo-N bond.Complexes 26 and 27 show 3D and 2D supramolecular organic framework,respectively.Complex 28 shows a 3D metal-organic framework formed by[V4O12]4 cluster and Zn ion.Complex 29 exhibits a discrete structure.The introduction of the ligands with different spacer length plays an important role in modifying the final structures.Complex 24 shows electrocatalytic properties in the reduction process of H2O2.Complexes 24-29 show high photocatalytic activity toward the degradation of MB and RhB under UV light irradiation. |
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