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Solvothermal syntheses, crystal structures, optical and thermal properties of new selenidogermanate and polyselenidogermanate
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文摘
New selenidogermanate salts [NH 4] 2[H 2N(CH 3) 2] 2Ge 2Se 6 (1) and [Ni(dien) 2] 2Ge 2Se 5(Se 2) (2) (dien = diethylenetriamine), and a selenidogermanate complex [{Ni(tepa)} 2(μ-Ge 2Se 6)] (3) (tepa = tetraethylenepentamine) were prepared by solvothermal reactions. Compounds 1 and 2 consist of discrete [Ge 2Se 6] 4− and [Ge 2Se 7] 4− anions, and NH\(_{4}^{+}\), [H 2N(CH 3) 2] + and [Ni(dien) 2] 2+ counter cations, respectively. The [Ge 2Se 6] 4− anion is constructed by two tetrahedral GeSe 4 building units via edge-sharing. In 2, two tetrahedral GeSe 4 units are linked by a corner and a Se–Se bond to form a polyselenidogermanate anion [Ge 2Se 7] 4− containing a five-membered ring Ge 2Se 3. The dimeric [Ge 2Se 6] 4− anion acts as a bridging ligand via the trans terminal Se atoms to link two [Ni(tepa)] 2+ cations, resulting in neutral complex 3. The Ni 2+ ion in 2 is coordinated by two tridentate dien ligands, while it is coordinated by a pentadentate tepa ligand and a selenidogermanate anion in 3. The different coordination environments of Ni 2+ ions indicate the influence of the denticity of ethylene polyamines on the formation of selenidogermanates in the presence of transition metal ions. The compounds 1–3 exhibit optical band gaps between 2.06 and 2.35 eV.

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