Solvothermal Synthesis And Structures Of The Chalcogenides Containing Lanthanide Metal

Extensive interest has been focused upon the Main Group chalcogenidometalates,due to their photoelectric properties. Recently, the solvothermal synthesis has beenbecoming an imporant route to the chalcogenidometalates. Introducing other metal ionsinto the solvothermal reactions, we can not noly synthesized ternarychalcogenidometalates, but also tune the structures and properties ofchalcogenidometalates via solvothermal reaction conditions and organic ligands to themetal ions. In this thesis, the solvothermal synthetic systems Ln/Ge/Se, Ln/Sn/S,Ln/Cu/Sn/S, Ln/Sb/Se were investigated in different ethylene polyamine solvents, and aseries of Ln-containing chalcogenidometalates were prepared under solvolthermalconditions. In this work, the major studies are as follows:1. The Ln-containing selenidogermanates [{Eu(tepa)(μ-OH)}2(μ-Ge2Se8)]n(1)[{Sm(tepa)(μ-OH)}2(μ-Ge2Se8)]n(2),[{Dy(en)3}2(μ-OH)2]Ge2Se6(3) were synthesizedby solvothermal method in tepa and en solvent, respectively. The influence of ethylenepolyamine on the selenidogermanates was discussed.2. The Ln-containing thiostannates [{Tb(tepa)(μ-OH)}2(μ-Sn2S6)]n·nH2O (4) and[{Dy(tepa)(μ-OH)}2(μ-Sn2S6)]n·nH2O (5) were synthesized by solvothermal method intepa solvent. The influence of ethylene polyamine on the thiostannates was discussed.3. Novel quaternary thiostannates [Hen]2[Ln(en)4(CuSn3S9)]·0.5en (Ln=La (6), Ce(7)) and [Hen]4[Ln(en)4]2[Cu6Sn6S20]·3en (Ln=Nd (8), Gd (9), Er (10)) weresynthesized in en solvent.6–7and8–9contain heterometallic [CuSn3S9]5–and[Cu6Sn6S20]10–clusters, respectively. The adamantine [CuSn3S9]5–anion coordinates toLn(III) center via a S atom in6and7. The influence of lanthanide contraction on theLn/Cu/Sn/S system was discussed. 4. The Ln-containing selenidoantimonates [Pr(dien)2(μ-η1,η2-SbSe4)]n(11),[Nd(dien)2(μ-η1,η2-SbSe4)]n(12),[Sm(dien)2(η2-SbSe4)](13),[Gd(dien)2(η2-SbSe4)](14),[Pr(trien)2(H2O)]SbSe4(15) and [Tb(trien)2]SbSe4(16) were synthesized bysolvothermal method in dien and trien solvents, respectively. The influences of ethylenepolyamines and lanthanide contraction on the compounds were investigated.5. The structures of the synthesized compounds were determined by single-crystalX-ray diffraction method and were characterized by IR and elemental analysis. Theirthermal stability and optical properties were also discussed.