| In this paper,fifteen new transition metal functional complexes metal–organic complexes?MOCs?based on Anderson/Keggin-type polyoxometalates and pyridine carboxylic and their derivatives have been successfully synthesized under the hydrothermal or solvothermal conditions and structurally characterized by single-crystal X-ray diffraction,powder X-ray diffraction?PXRD?,IR spectra and thermogravimetric analyses?TGA?.The adsorption behaviors of organic dyes,photocatalytic and electrochemical properties for the title complexes were investigated in detail.1.The 3-?2-pyridinecarboxylic acid amido?pyridine was used as organic ligand to assemble with Anderson-type polyanions and different transition metal ions.As a result,eleven new transition metal functional complexes metal–organic complexes?MOCs?have been successfully synthesized under the hydrothermal or solvothermal conditions.It is worth noting that the HPCAP ligand in complex 1 was in-situ transformed to the PCAP'ligand.{?H2PCAP'?2[CrMo6?OH?5O19]}·H2O?1?{Cu?HPCAP?2[CrMo6?OH?6O18]}·2H2O?2?{Cu3?PCAP?2[CrMo6?OH?5O19]?H2O?3?DMF?2}·4H2O·2HCHO?3?{Cu3?PCAP?2[CrMo6?OH?6O18]Cl?H2O?5}·10H2O?4?{Co3?PCAP?2[CrMo6?OH?5O19]?H2O?6}·9H2O·HCHO?5?{Zn3?PCAP?2[CrMo6?OH?5O19]?H2O?6}·6H2O?6?{Cu3?PCAP?2[AlMo6?OH?5O19]?H2O?6}·6H2O?7?{Ni3?PCAP?2[NiMo6?OH?5O19]?H2O?6}·8H2O?8?{Co3?HPCAP?2[CrMo6?OH?6O18]2?H2O?10}·7H2O·2CH3CH2OH?9?{Co3?HPCAP?2[AlMo6?OH?6O18]2?H2O?10}·6H2O?10?{Zn4?PCAP?2[CrMo6?OH?6O18]2?H2O?12}·4H2O?11?[HPCAP=3-?2-pyridinecarboxylicacidamido?pyridine,PCAP'=3-?pyridinecarboxylic acid?amido pyridine]Complexes 1 and 2 were obtained with H2O as solvent.When the pH value was adjusted to about 4.2,colorless block crystals of 1 were obtained,which was exhibits a 3D supramolecular network based on CrMo6 anions and protonated H2PCAP'molecules via hydrogen bonds.Complex 2 share the same experimental materials with 1 except that pH value was adjusted to about 1.5.The 3D supramolecular framework of 2 was constructed from the1D Cu-PCAP inorganic chains and the discrete CrMo6 polyanion.Complexes3-11 were synthesized with different mixed solvents.In complex 3,the CrMo6 anions acting as the inorganic bridging ligand link the 1D[Cu3?PCAP?2]n4n+chain to construct a 2D layer.Complexes 4-8 show similar3D frameworks.Two orientations of metal-organic loops[M2?POM?2]can be observed,which directly extend the 1D M-POM chains into the 3D networks with a 3,3,4,4-connected{42·123·14}{42·6}2 topology.Complexes 9 and 10are isostructural,the 1D Co-POM inorganic chain,[Co2?PCAP?2]binuclear loop unit and discrete polyanion connect with each other by hydrogen bonding interactions to form a 1D ladder-like supramolecular dual chain.Complex 11 is a supramolecular layer constructed from the[Zn2?CrMo6?2]and[Zn2?PACP?2]binuclear clusters.The structural diversities show that solvents,metal ions and the pH value of reaction play key roles in the construction of various architectures.Additionally,in order to investigate the electrochemical properties of Anderson-type POM-based MOCs,complex 4has been taken as an example.The adsorption behaviors of the title complexes for organic dyes were investigated in detail.2.By introducing the pyridine carboxylic and their derivatives ligands into Keggin/Anderson-type polyoxometalates systems,four new POMs-based MOCs have been successfully synthesized under hydrothermal conditions.[Ag12?INA?8(VW11VIWVO40)?H2O?2]·VO2?12?{[Ag5?INA?5?HINA?][H3PMo12O40]?H2O?]}·H2O?13?[Ag10?NCA?4(PW9V?W3VO40)?H2O?4]?14?[Cu4??3-OH?2L2?H2O?4][CrMo6?OH?5O19]?15?{INA=isonicotinicacid;NCA=nicotinicacid;L=6-?2,3-Dihydro-oxazolo[4,5-b]pyrazin-2-yl?-nicotinic acid}Complex 12 exhibits a 3D metal-organic framework constructed from[VW11VIWVO40]4–-based 2D inorganic layers and 1D[Ag3?INA?2]n chains.Interestingly,a discrete 1D[Ag3?INA?2]n chain and VO2 molecule alternately distribute in the channels of the POMOF.In addition,the starting reagent[PW12O40]3–in 12 was converted into[VW11VIWVO40]4–in the presence of NH4VO3.13 shows a 3D architecture based on 1D fishbone-like[Ag5?INA?5?HINA?]n metal-organic chains and[PMo12O40]3-anions.The 3D metal-organic framework of complex 14 is constructed from the[Ag10?NCA?4]n6n+layers and[PW9V?W3VO40]6-polyanions.Complex 15 is a3Dsupramolecularframeworkderivedfromthe2D[Cu4??3-OH?2L2?H2O?4]n4n+network and[PW9V?W3VO40]6-polyanions via hydrogen-bonding interactions,notably,the L ligand in 15 was firstly introduced into the POM-based MOCs.The electrochemical,dye adsorption behaviors and photocatalytic properties of the title complexes have been reported. |
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