Solvothermal Syntheses And Crystal Structures Of IVA Metal Chalcogenides

The solvothermal reaction in ethylene polyamine is becoming an important route to the synthesis of IVA group chalcogenidometalates containing the transition metal or lanthanide metal complexes. The organic amine acts as not only the solvent of the reaction, but also the ligand to the transition metals or lanthanide metals, which endues chalcogenidometalates with structural diversity. In this thesis, the solvothermal synthetic systems M/Q(M=Ge, Sn; Q=S, Se) were investigated in the presence of transition metals or lanthanide metals in ethylene polyamine solutions. The chalcogenidogermanates and thiostannates containing transition metal complexes, and chalcogenidostannates containing lanthanide metal complexes were prepared under solvothermal conditions. The synthesized compounds were measured and characterized by X-ray diffraction, elemental analysis and IR. The thermogravimetric (TG) analysis and optical absorption spectra were also measured. The influence of ethylene polyamine and transition metal and lanthanide metal ions on the chalcogenidogermanates and chalcogenidostannates were discussed. In this work, the major studies and results as follows:1. The chalcogenidogermanates [{Co(tepa)}2(μ-Ge2S6)](1)[{Mn(tepa)}2(μ-Ge2Se6)] (2) and [{Fe(tepa)}2(μ-Ge2Se6)] (3) with the same structure of dimeric [Ge2S6]4- and [Ge2Se6]4- anion were synthesized by solvothermal method in tepa solvents, respectively.2. The transition metal-contained selenidostannates [Ni(en)(trien)]2Sn2Se6 (4) [Co(en)(trien)]2Sn2Se6 (5) were synthesized by solvothermal method in en and trien mixtural solvent. [Ni2(trien)2(μ-trien)]Cl4·2H2O (6) were synthesized by solvothermal method in trien solvent. It shows different solvent effect of trien from en and en/trien on the solvothermal synthesis. Perhaps the large cation [Ni2(trien)2(μ-trien)]2+ prevented formation of the [Sn2Se6]4- anion in the trien solvent. 3. The lanthanide-contained selenidostannates [{La(en)4}2(μ-Se2)]Sn2Se6(7),[{Ln(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞(Ln=La(8),Ce(9),N d(10)) and [Hdien][Gd(dien)2(μ-SnSe4)](11) were synthesized by solvothermal method in en or dien solvents. Exploring the influence of ethylene polyamines and lanthanide metal size on the compounds.4. The lanthanide-contained compounds [Eu2(en)6(μ2-OH)2]Sn2S6(12), [Sm(dien)3]2[(Sn2S6)Cl2] (13) and [Eu(dien)3]2[(Sn2S6)Cl2](14)were synthesized by solvothermal method in en or dien solvents. Exploring the influence of ethylene polyamines on the compounds.5. The synthesized chalcogenidogermanates and chalcogenidostannates were characterized by elemental analysis, IR and X-ray crystallographic, and their thermal stability and optical properties were also investigated.