| Organic hybrid iodoplumbates have a wide range of application prospects in the fields of nonlinear optics,ion exchange,semiconductors and photocatalysis due to their structural diversity,and they have also received much attention.The synthetic methods of the organic hybrid iodoplumbate include hydrothermal synthesis method,diffusion method,solvothermal method,ect.In this paper,protonated organic cations,quaternary ammonium salts and complex cations containing transition metal complex ions were used as structure directing agents in the reaction system of organo-hybrid iodoplumbates.A variety of inorganic and organic iodoplumbates with different structures were synthesized and characterized by changing synthesis methods,temperature,solvent,etc.The photocatalytic degradation of organic dyes was studied1.The compound[PhCH2NEt3]2Pb2l6(1)was synthesized in the PbI2/HI system with the quaternary ammonium salt PhCH2NEt3Cl as the structure directing agent.Under the same conditions,the compound[Hpya]2Pb2I6(2)was synthesized by protonated pya insteaded of PhCH2NEt3Cl.The compound[H2tmdp]Pb2I6·DMF(3)was synthesized under normal temperature conditions by using the flexible bis-amino ligand tmdp as a structure directing agent.The anion moiety of compound 1-3 is a[Pb2I6]n2-polymerized anion chain formed by coplanar formation of PbI6 octahedron.The 2D layered compounds[H2tmdp]2Pb7I18(4)and(H2tmdp)4(Hpyd)2(Me2NH2)Pb6I22(13)·8H2O(5)were synthesized by solvothermal method.The anion of compound 4 was determined by The PbI6 octahedron forms a[Pb7I184-]n polymeric anion layer with common apex and co-edge.The anion portion of compound 5 is formed by PbI6 octahedron with common apex and face-sharing composited[Pb612210-]n polymeric anion layer.The synthesis conditions affect the polymerization mode of iodoplumbate octahedron,which further affects the anion structure of iodoplumbates.The 2D layered[Pb7I18]4-and[Pb6I22]10-ions are new Pb-I binary structure ions.The photocatalytic degradation of organic dyes by compound 3-5 have tested.Compound 3-5 has catalytic activity for methylene blue(MB)and rhodamine B(RhB).The degradation rate of MB of compound 3-5 was 74%,94%and 100%when visible light irradiation was 2.5 h,the catalytic activity of dye MB was 5>4>3,and the degradation rate of RhB was 5 h after visible light irradiation.The catalytic activity of compound 3-5 for MB was higher than that of RhB,which were 23.3%,42.7%,and 51.3%,respectively.2.Iodoplumbates 6-11 was synthesized by using TM ion as structure directing agent:[Co(dien)2]Pb2I6·H2O(6),[Mn(dien)2]Pb2I6·H2O(7),[Ni(dien)2]Pb2l6·H2O(8),[Co(en)3]Pb2l6(9),[Ni(en)3]Pb2l6(10)and[Ni(en)2]2Pb3I10(11).For the first time,the compound[Ni(tmcyclam)][PbI3]2·DMF(12)was synthesized from tetracycline macrocyclic tmcyclam as metal ion ligand in DMF solvent,and the compound[Ni(tmcyclam)]2[Pb5I14(DMSO)2](13)was synthesized in DMSO solvent.Compounds 6-13 form 1D[Pb2I62-]n,[Pb3I104-]n,[PbI32-]n and[Pb5I14(DMSO)24+]n anion chain by different PbI6 octahedron combination of apex,co-edge and face-sharing.The photocatalytic degradation activities of compounds 8 and 11-13 on organic dyes MB,CV(crystal violet)and MO(methyl orange)were studied.When the illumination time was 2.5 h,the degradation efficiency of compounds 8,11 and 13 for MB respectively was 82.8%,85.3%and 100%,but the degradation rate of MB for compound 12 was 94.2%,the decomposition rate of CV for compound 12 was 96.7%and the degradation rate for MO was 79.6%.The experimental results show that iodoplumbates 12 and 13 containing planar structure[Ni(tmcyclam)]2+have high catalytic activity for degrading dyes,compounds 12 and 13 have higher catalytic activity for organic dyes than compounds 8 and 11.The photocatalytic activity sequence of 12 was MB>CV>MO.3.The structure of the compound was determined by X-ray single crystal diffractometer.The compounds were characterized by infrared spectroscopy,XRD,TG and elemental analysis.The thermal stability and optical properties of the compounds were determined. |
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