| In recent years,organic hybrid haloargentates have received considerable attention owing to their various structural topologies and their potential applications in photoelectic,semiconductor,ion exchange,photoluminescence and photocatalytisis.Organic hybrid haloargentates can be synthesized by a variety of methods,such as:room temperature static method,room temperature diffusion method and solvothermal synthesis method.In addition,there are many factors influencing the structure and composition of target compounds,for examlpe:synthetic method,pH value,solvent,structure directing agent?SDA?and so on,among them,SDA plays an obvious role.Introducing transition metals or lanthnide metals into organic hybrid haloargentates has led to novel multinary haloargentates,which makes us studying on structures and properties about organic hybrid haloargentates more deeply.In this paper,a series of haloargentates were synthsized and characterized by introducing a different kinds of SDAs while changing solvents,reaction conditions and synthesis methods.1.Six bromoargentates with 0-D,1-D and 3-D structures were synthesized by TMm+-phen ions as structure directing agents:[TM?phen?3]2Ag13Br17?2DMSO?3H2O?TM=Fe?1?,Co?2?,Ni?3??,[Cu?phen?2?Br?]AgBr2?4?,[Fe?phen?3]Ag2Br4?DMF?5?and[Fe?phen?2?Cl?2]2Ag2Br4?6?.In AgNO3/Na2S2O3/KBr system,by introduction of the organothione ligand mimt,[Ag3?mimt?3Br3]?7?and[Ag8??8-S??mimt?12]?NO3?6?8?were synthesized in DMSO and DMF solvents,respectively.By introduction of the organothione ligand ctu,[Ag4?ctu?5Br4]?9?and Ag?ctu?2Br?10?were synthesized in DMSO and DMF solvents,respectively.In 7,9 and 10,organothione ligand and Br-both coordinate to Ag+.Although Ag+is not combined with Br-in 8,compound[Ag8??8-S??mimt?12]?NO3?6?8?is the first cubic nuclear cluster cationic compound with organothione ligand and?8-S2-ligand.The photocatalytic activity of some compounds was studied.Compounds 4 and 6 have the strongest photocatalytic activity for CV.The photocatalytic selectivity of compounds 1,4 and 6 for MB and RhB were further studied.Compound 1 has no obvious selectivity for CV,MB and RhB.Compound 4 and 6 showed strong photocatalytic activity in MB,while the photocatalytic activity of RhB was weak.2.The organic hybrid haloargentates containing Mn2+complex ions[Mn?4,4'-bipy??DMF?3?H2O?]Ag5I7?4,4'-bipy?11?,[Mn?4,4'-bipy?2?DMSO?4]2Ag11I15?12?,[Mn?4,4'-bipy??DMSO?2?H2O?2]Ag10I12?2DMSO?2H2O?13?,[Mn?4,4'-bipy??DMF?3?DMSO?2?H2O?]Ag10I14?2H2O?2DMF?14?,[Mn?2,2'-bipy?2?DMF?2Ag5I7]?15?and[Mn?2,2'-bipy?2?DMSO?2]Ag5I7?16?were prepared in DMF/H2O,DMSO/H2O,DMF/DMSO/H2O mixed solvents,respectively.Among them[Ag11I154-]n and[Ag10I144-]n represent new members of binary iodoargentate aggregates.The affection of solvent on structures was discussed.The fluorescence properties of 11-14were studied.The photocatalytic activity of compounds 11,12 and 15 were studied.In contrast,compound 15 has the strongest photocatalytic activity on CV.The photocatalytic selectivity of compounds 11,12 and 15 was further studied.The photocatalytic activity of11,12 and 15 on RhB is much weaker than that of CV.3.Organic hybrid lanthanide iodoargentates[Ln?DMSO?8]4Ag22I34?2H2O?Ln=La?17?,Ce?18??,[Ln?DMSO?8]Ag7I10?Ln=Eu?19?,Tb?20?,Dy?21??and[Yb?DMSO?7]Ag5I8?22?were synthesized by a diffusion method.It is found that the contraction effect of lanthanide has obvious influence on the structure of the compound.The fluorescence properties of compounds 19 and 20 were studied and the characteristic emission spectrogram was obtained.The photocatalytic activity of 19-21 on MB was studied,and the photocatalytic activity of 19 and 21 was better than that of 20.The photocatalytic selectivity of the compounds 19-21 was further studied.In contrast,compound 21 has the highest photocatalytic efficiency for MB and CV,relatively weak photocatalytic efficiency for RhB,and the weakest photocatalytic efficiency for MO.The photocatalytic activity of 19 and 20 on the three dyes of CV,MO and RhB was similar but relatively weaker than that of 21.4.Hybrid organic Pb-Ag hetermetallic iodides[?en?2?PbAgI3?]2n·nH2O?23?,[?pda?2?PbAgI3?]n?24?,[?tmeda??PbAgI3?]n?25?,[?trien??PbAgI3?]n?26?,[?tepa??PbAg2I4?]n?27??[{?dien?3?CO3?}2(Pb6Ag8I15)]n In?28?were prepared by the reaction of PbI2,AgI?or Ag2CO3?and KI with different polyamines with coordination capacity in DMF solution.28 is the first one that has?3-CO32-as a trident ligand coordinating with Pb.The structuring directing influence of ethylene polyamine on Pb-Ag hetermetallic iodides was discussed.In these six compounds,ethylene polyamine coordinating with Pb2+have enhanced the structural stability of Pb-Ag-I ternary compounds.The fluorescence properties of solid samples 27 and 28 were studied.When excited by the light of 280 nm,the compounds 27 and 28 emit intense fluorescence at 518 nm and 539 nm respectively.For 28,the weak shoulder peak fluorescence was also emitted at 582 nm.5.These compounds were determined by X-ray sigle crystal diffactometer.And these compounds were characterized via infrared spectrometer and elemental analyzer.The thermal stability and optical properties of the compounds were analyzed. |
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