Solvothermal synthesis, crystal structures and properties of three new thiogermanates: the only example of the thiogermanate anion [Ge2S6]4− as a bridging ligand to a lanthanide complex ionElectronic Supplementary Information (ESI) available: crystal data in CIF format and TG. CCDC reference numbers 860863 (1), 860864 (2) and 860865 (3). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2ce25082a

• Main Authors: Liu, Xing, Hu, Feilong, Zhou, Jian, An, Litao, Liang, Dawen, Lin, Jianwu
• Format: Article
• Language: English
• ISSN: 1466-8033
• DOI: 10.1039/c2ce25082a

Three new thiogermanates, (trenH 2 ) 2 [Ge 2 S 6 ] ( 1 , tren = tris(2-aminoethyl)amine), [Eu(dien) 3 ] 2 [Ge 2 S 6 ]Cl 2 ( 2 , dien = diethylenetriamine) and [Y 2 (tepa) 2 (μ-OH) 2 (μ-Ge 2 S 6 )](tepa) 0.5 ·H 2 O ( 3 , tepa = tetraethylenepent-amine), were solvothermally synthesized and characterized. Both 1 and 2 are composed of discrete [Ge 2 S 6 ] 4− anions, while 3 contains a bridging [Ge 2 S 6 ] 4− anion as a μ 2 -ligand with trans terminal S atoms linking [Y 2 (OH) 2 (tepa) 2 ] 4+ groups, which is the only example of germanium chalcogenide anions acting as bridging ligands to a lanthanide complex ion. The optical absorption spectra indicate that they are wide band-gap semiconductors and their thermal stabilities have been investigated by thermogravimetric analyses (TGA). The linkage of dinuclear complex cation, [Y 2 (tepa) 2 (μ 2 -OH) 2 ] 4+ , and bridging anion, [Ge 2 S 6 ] 4− , gives a 1-D neutral chain, [Y 2 (tepa) 2 (μ-OH) 2 (μ-Ge 2 S 6 )] n , which alternately stacks in a crossed manner to form a 3-D network with 1-D channels.