Synthesis And Structures Of Chalcogenides And Halides Containing Lanthanide Complex Cations

The Main Group chalcogenidometalates and halometallates have gained increasing interest because of their structural diversity and potential applications.The solvothermal and templating synthesis are important routes to syntheses chalcogenidometalates and halometallates. The structures and properties of chalcogenidometalates and halometallates can be tuned by ligands, reaction conditions and structure-directing agents. In this thesis, three systems Ln/As/S, Ln/Sb/Se and Ln/Pb(Ag)/I(Ln= Lanthanide) were investigated, and a series of lanthanide chalcogenidometalates and halometallates were prepared and characterized.1. Two types of lanthanide thioarsenates with the general formulae [Ln(dien)2(μ-1κ,2κ2-As S4)]n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien)2(1κ2-As S4)] [Ln=Tb(4), Dy(5), Ho(6)] were synthesized by solvothermal method in dien solvent. The effect of lanthanide contraction on the coordination modes of the As S4 ligand to the Ln3+ centers was discussed.2. Four gadolinium selenidoantimonates [Gd(trien)2]Sb Se4(7), [Gd(dien)(trien)(1κ-Sb Se4)](8), [H2tepa][Gd(tepa)(μ-OH)(1κ-Sb Se4)]2(9) and [Gd(peha)(1κ2-Sb Se4)]2(10)were prepared by solvothermal reactions in trien, dien+trien, tepa and peha solvents respectively. The influence of ethylene polyamine on the coordination modes of the Sb Se4 ligand to the Gd3+ centers was discussed.3. Iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31(11) and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(12), Pr(13)] were prepared by the reactions of Pb I2 or Ag NO3 and KI in DMF solvent, respectively. The same reactions in the absence of Ag NO3 and Pb I2 obtained heterometallic iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(14), Pr(15)]. Compound 11 contains a 1D zigzag [Pb11I319-]n chain, While compounds 12 and 13 contain a [Ag6I12]6- building block. And compounds 14 and 15 contain a ternary one-dimensional polymeric [Pb3Ag10I22]6- anion. The influence of the Ln3+ ions and counterion’s charges on the iodometallate anion were discussed.4. The synthesized chalcogenidometalates and halometallates were determined by single-crystal X-ray diffraction method and characterized by elemental analysis and IR. Their thermal stability and optical properties were also discussed.