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Two new organic hybrid thiogermanates [Ni(dien) 2 ](H 2 dien)Ge 2 S 6  (1, dien = diethylenetriamine) and [Ni(teta) 2 ] 2 Ge4S 10  (2, teta = triethylenetetramine) were synthesized under solvothermal conditions. 1 contains a [Ni(dien) 2 ] 2+  complex cation, a protonated dien molecule and a [Ge 2 S 6 ] 4−  dimeric anion, while 2 consists of discrete [Ge 4 S 10 ] 4−  adamantane-like cluster anions with [Ni-(teta) 2 ] 2+  complex cations as counter ions. The [Ge 4 S 10 ] 4−  anion is composed of four nearly tetrahedral Ge 4+  centers to which are bonded four terminal atoms and six bridging S atoms. Luminescence studies have shown that 2 exhibits an emission at 468 nm.

Two Organic Hybrid Thiogermanates [Ni(dien) 2 ] 2 (H 2 dien)Ge 2 S 6 and [Ni(teta) 2 ] 2 Ge 4 S 10