| The solvothermal reaction in organic amine is becoming a versatile route to the synthesis of p 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. So the organic amine plays an important role on the formation of the chalcogenidometalates. In addition, the solvothermal reaction conditions such as the temperature and concentration also have much influence on the syntheses. In the thesis the Ge/Se and Sb/Se synthetic systems in organic amine were investigated under mild solvothermal conditions. We have synthesized the first examples of the selenidogermanates containing transition metal complexes from the Ge/Se system. We explored the influence of temperature and organic amines on the Sb/Se system, and have synthesized a series of selenidoantimonates containing transition metal and lanthanide metal complexes. The crystal structure determination shows that the reaction temperature influences the valent state of Sb atom in the presence of transition metal complexes. The higher temperature is preferable to the formation of the selenidoantimonates(V) compounds. In the case of lanthanide metal complexes, the tetrahedral [SbSe4]3? ion can be controlled to coordinate with the La3+ and Eu3+ ions by using different ethylene polyamines as the second ligands. In this work, the major studies and results as follows:1. The chalcogenidogermanates [Mn(en)3]2Ge2Se6(1) and [Fe(dien)2]2Ge2Se6(2) with the same structure of dimeric [Ge2Se6]4- anion were synthesized by solvothermal method in en and dien solvents, respectively.2. The transition metal-contained chalcogenidoantimonates [Ni(dien)2]2Sb2Se6(3), [Mn(dien)2]2(SbSe4)(Cl)(4), [Co(dien)2]2(SbSe4)(Br)(5) and [Co(dien)2]3(SbSe4)2 (6)。 were synthesized by solvothermal method in dien solvent.Exploring the influence of the temperature on the chalcogenidoantimonates.3. The lanthanide-contained chalcogenidoantimonates [La(en)2(dien)(η2-SbSe4)] (7), [La(dien)2(μ-η1,η2-SbSe4)](8), [La(trien)2(H2O)]SbSe4(9), [La(en)(trien)(μ-η1,η2- SbSe4)](10), [Eu(en)2(dien)(SbSe4)](11), [Eu(en)(trien)(η2-SbSe4)](12) and [Eu(dien)2(η2-SbSe4)](13) were synthesized by solvothermal method in dien, trine, en/dien or en/trien mixtural solvents. Exploring the influence of ethylene polyamines on the coordination of tetraselenidoantimonate [SbSe4]3- anion with trivalent lanthanide ions.4. The synthesized chalcogenidometalates were characterized by elemental analysis, IR and X-ray crystallographic, and their thermal stability and optical properties were also investigated. |
PDF Full Text Request