Study On Syntheses,Structures And Properties Of Organic Hybrid Lodoargentates And Lodocuprates

Organic hybrid iodoargentates and iodocuprates have been intensively investigated because of not only structural diversity but also the applications in semiconductors,photochromic behavior,photocatalysis,ion exchange and photocurrent.The two main methods for the preparation of organic hybrid iodoargentates and iodocuprates are room temperature evaporation method and solvothermal synthesis method.Five novel heterometallic Pb-Ag iodides and six iodoargentates were synthesized by introducing transition metals into Pb/Ag/I and Ag/I systems,respectively.Three iodocuprates with different organic cations as structure directing agents were synthesized.1.Heterometallic Pb-Ag iodides including[TM(en)3]PbAgI5[TM=Mn(1),Fe(2),Zn(3)],[Ni(en)2]PbAg2I6(4)and[Ni(dien)(MeCN)3]Pb3Ag2I10)·MeCN(5)were synthesized by introducing transition metals into Pb/Ag/I system under solvothermal conditions.In 1-3,one AgI4 tetrahedron and one PbI6 octahedron are connected via edge-sharing into the ternary heterometallic 1-D polymeric anion[PbAgI5]n2n-.In 4,two AgI4 tetrahedra share a common edge to form the bimeric Ag2I6 unit.The Ag2I6 unit connected one PbI6 octahedron via iodine atoms to form a 2-D[PbAg2I6]n2n-layer.In 5,AgI4 tetrahedra and PbI6 octahedra are interlinked with co-edge to form a 2-D[Pb3Ag2I10]n2n-waved layer.The anions in compounds 1-5 are new Pb-Ag-I ternary structure ions.Compounds 1,3 and 5 were used as catalysts to explore their photocatalytic properties by degrading the organic dye methylene blue(MB).The degradation ratios towards MB reach 68.7%,60.0%and 100.0%exposed to visible light for 3 h using compounds 1.3 and 5 as the photocatalysts,respectively.Meanwhile,the photocatalytic degradation mechanism of MB over compounds 3 and 5 was investigated.The ·O2-radical is the main reactive species in the photodegradation of MB over compound 3.while all ·OH.·O2-and h+ reactive species play an important role in the photocatalytic reaction over compound 5.The photocurrent curves of compounds 3 and 5 were tested.The photocurrent intensity was 0.038 nA for 3 and 0.13 nA for 5.respectively,indicating that compound 5 had better photoelectric response.2.Six iodoargentates namely[Mn(DMSO)2(2,2'-bpy)2]Ag5I7(6).[Mn(DMF)2(2,2'-bpy)2]Ag5I7(7),[Zn(DMF)2(2,2'-bpy)2]Ag5I7(8),[{Cd(2,2'-bpy)2}2(?4-Ag2I6)](9),[{Zn(DMF)2(H20)2}(4,4'-bpy)1.5]Ag5I7·2DMF(10)and[Zn(DMSO)2(H2O)2(4,4'-bpy)2]Ag10I12·2H2O·2DMSO(11)were synthesized in TM/bpy/AgI/KI system with different solvents.The charge balance TM2+-2,2'-bipy(TM=Mn,Zn)complex cations modified by small ligands via solvating in different polar solvents lead to formation of ?-[Ag5I72-]n chains in compounds 6-8,while the[Cd(2,2'-bpy)2]2+ unit affords a binuclear neutral complex 9 with a novel tetradentate?-Ag2I6 ligand.The solvated Zn2+-4,4'-bpy complex cation results ?-[Ag5I72-]n and[Ag10I122-]n chain-like anions in 10 and 11,respectively.All the polymeric ?-[Ag5I72-]n,?-[Ag5I72-]n,?4-Ag2I6 and[Ag10I122-]n units are fonned by the primary tetrahedral AgI4 units via corner-or edge-sharing.The degradation rate of CV was 90.53%and 93.18%after exposing to visible light for 6 h when compounds 8 and 10 were used as photocatalysts,respectively,while the degradation rate of compound 9 only reach 28.12%under the same condition.Compounds 8 and 10 show effective photocatalytic activities.The photocatalytic degradation mechanism of 8 and 10 on CV was discussed.All·O2-,h+and OH play a key role in the degradation of CV by compound 8,while OH is the main active species in the degradation of CV by compound 10.The photoelectric response properties of compounds 8 and 10 were measured.Under 150 W xenon light source,the photocurrent intensity was 1.65 nA for 8 and 10 nA for 10,respectively.The results indicate that compounds 8 and 10 have good electron transport efficiency,which is beneficial to accelerate the degradation of organic dyes.3.In CuI/HI reaction system,[dedabco]4(Cu4I8)2·H2O(12),[H2tmdp]2(Cu2]5)(?)·H2O(13)and[HDCE]Cu2I3(14)were synthesized with diethyl dabco,protonated tmdp and protonated DCE as the structural directing agent,respectively.The photocatalytic degradation activities of compounds 12-14 on MB were investigated.When visible light irradiation was 6 h.the degradation efficiency on MB was 44.63%for 12,48.35%for 13 and 92.18%for 14,respectively.The results exhibit iodoargentate 14 has the highest catalytic activity on MB.The photocurrent intensity of compound 14 can reach 0.0375 nA under xenon lamp light source,showing that it has good photoelectric response4.Using X-ray single crystal diffractometer determined the crystal structures The compositions of the compounds were characterized by elemental analysis,XRD and IR spectroscopy,and investigated the optical properities and thermal stability of them.