Two Novel Adamantane‐Like Thio/Selenidogermanates with Complex Cations

Two new thio/selenidogermanates [Ni 2 (μ‐teta)(teta) 2 ]Ge 4 S 10 ·H 2 O ( 1 ) and [Ni(teta) 2 ] 2 Ge 4 Se 10 ·0.5H 2 O ( 2 ) (teta = triethylenetetramine) were solvothermally synthesized and structurally characterized. Both 1 and 2 consist of discrete [Ge 4 Q 10 ] 4– (Q = S, Se) adamantane‐like anions with complex cations as counterions. The [Ge 4 Q 10 ] 4– (Q = S, Se) anions are composed of four nearly tetrahedral Ge IV atoms to which are bonded four terminal Q atoms and six bridging Q atoms. Although numerous thio/selenidogermanates with complex cations have been reported, their anions are usually dimeric [Ge 2 Q 6 ] 4– (Q = S, Se) species. 1 and 2 represent the rare examples of the adamantane‐like thio/selenidogermanates with complex cations. The optical absorption spectra indicate that 1 and 2 are wide‐band‐gap semiconductors.