Issue 40, 2012

The first μ-Ge2Se8ligand to lanthanide(iii) centers: solvothermal syntheses and characterizations of lanthanide selenidogermanate complexes with a pentadentate polyamine as a co-ligand

Abstract

Solvothermal reactions of elements Ge and Se with Ln2O3 in a pentadentate polyamine, tetraethylenepentamine (tepa), produced novel neutral lanthanide–selenidogermanate polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n (Ln = Eu 1, Gd 2, Dy 3). The reaction with Dy2O3 in ethylenediamine (en) afforded an ionic selenidogermanate [{Dy(en)3}2(μ-OH)2]Ge2Se6 (4). In compounds 1–3, the Ln3+ ions are coordinated by a tepa and two OH ligands to form binuclear [{Ln(tepa)}2(μ-OH)2]4+ fragments. Two GeSe4 tetrahedra are linked through two Se–Se bonds to form a novel [Ge2Se8]4− unit containing a six-membered Ge2Se4 ring in the chair conformation. The [Ge2Se8]4− unit acts as a bridging ligand via the trans terminal Se atoms to interlink the [{Ln(tepa)}2(μ-OH)2]4+ fragments into one-dimensional polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n. Compounds 1–3 are the first examples of solvothermally prepared lanthanide complexes with a selenidogermanate anion as a ligand. The [Ge2Se6]4− anion in 4 is composed of two GeSe4 tetrahedra sharing a common edge, and is charge compensated by a [{Dy(en)5}2(μ-OH)2]4+ complex cation. The formation of the [Ge2Se8]4− and [Ge2Se6]4− anions and their behavior towards lanthanide ions in 1–4 show the significant influence of ethylene polyamines on the solvothermal synthesis of Ln selenidogermanates.

Graphical abstract: The first μ-Ge2Se8 ligand to lanthanide(iii) centers: solvothermal syntheses and characterizations of lanthanide selenidogermanate complexes with a pentadentate polyamine as a co-ligand

Supplementary files

Article information

Article type
Paper
Submitted
03 May 2012
Accepted
15 Aug 2012
First published
16 Aug 2012

Dalton Trans., 2012,41, 12439-12445

The first μ-Ge2Se8 ligand to lanthanide(III) centers: solvothermal syntheses and characterizations of lanthanide selenidogermanate complexes with a pentadentate polyamine as a co-ligand

R. Chen, W. Tang, J. Liang, W. Jiang, Y. Zhang and D. Jia, Dalton Trans., 2012, 41, 12439 DOI: 10.1039/C2DT30960B

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