Synthesis, Structures, and Light‐Induced Transformation of Keto‐Functionalized Selenidogermanate Complexes

A double‐decker (DD) type selenidogermanate complex with C=O functionalized organic decoration, [( R 1 Ge 4 )Se 6 ] ( 1 , R 1 = CMe 2 CH 2 COMe), was synthesized by reaction of R 1 GeCl 3 with Na 2 Se, and subsequently underwent a light‐induced transformation reaction to yield [Na(thf) 2 ][( R Ge IV ) 2 ( R Ge III )(Ge III Se)Se 5 ] ( 2 ). Similar to the observations reported previously for the Sn/S homologue of 1 , the product comprises a mixed‐valence complex with a newly formed Ge–Ge bond. However, different from the transformation of the tin sulfide complex, the selenidogermanate precursor did not produce a paddle‐wheel‐like dimer of the DD type structure, but led to the formation of a noradamantane (NA) type architecture, which has so far been restricted to the Si/Se and Ge/Te elemental combination.