Room‐Temperature Synthesis of Three Compounds Featuring the [Ge₄S₁₀]^4– Anion from a Water‐Soluble Thiogermanate Precursor

Abstract

Applying a new synthetic approach in which transition metal complexes and a thiogermanate source are in different liquid phases resulted in crystallization of three new compounds with the adamantane-like [Ge 4 S 10 ] 4anion at room temperature. In the crystal structure of [Ni(cyclam)] 3 [Ni-(cyclam)(H 2 O) 2 ][Ge 4 S 10 ] 2 ·21H 2 O (I, cyclam = 1,4,8,11-tetraazacyclotetradecane), the two different Ni 2+ -centered complexes and two unique [Ge 4 S 10 ] 4anions are joined by H-bonding interactions with a water cluster composed of condensed pentameric and hexameric rings. The compound {[Mn(2,2′-bipy) 2 -(H 2 O)] 2 Ge 4 S 10 }·3H 2 O (II, bipy = bipyridine) also contains the [a] Christian-Albrechts-Universität zu Kiel,

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…In a unique synthetic approach, it was also shown that those clusters can be made electrochemically using a Sn2Se3 cathode in a [Et4N]Br electrolyte solution in ethane-1,2-diamine to form [Et4N]4[Sn4Se10] (517) [283] The known Ge4E10 cluster compounds are often used as reactants in ion exchange reactions (method L) to introduce a desired functionality or structural template to the compound, such as larger ammonium cations forming lamellar structures (521-538), [284][285][286] organic molecules (539-546) [287][288][289][290][291] or transition metal complexes with interesting optical properties(547-551). [289,292,293] The family of clusters with metal complex counterions could also be expanded by starting from elements and binary precursors in solvothermal reactions (method B) to not only obtain more Ge clusters (552-556), [294][295][296][297] but also Sn congeners as well as rare earth containing examples(557-562). [298][299][300] In one case, the addition of antimony to such a reaction mix of GeO2 and elemental sulfur led to the formation of a compound with two distinct clusters, [(Me)2NH2]6[Ge2Sb2S7][Ge4S10] (563), one adamantane-type and another ternary molecule with noradamantane like topology.…”