Two Novel Adamantane‐Like Thio/Selenidogermanates with Complex Cations

Two new thio/selenidogermanates Ni₂(μ‐teta)(teta)₂]Ge₄S₁₀·H₂O ( 1 ) and Ni(teta)₂]₂Ge₄Se₁₀·0.5H₂O ( 2 ) (teta = triethylenetetramine) were solvothermally synthesized and structurally characterized. Both 1 and 2 consist of discrete Ge₄Q₁₀]^4– (Q = S, Se) adamantane‐like anions with complex cations as counterions. The Ge₄Q₁₀]^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 Ge₂Q₆]^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.