Two Novel Adamantane‐Like Thio/Selenidogermanates with Complex Cations

Abstract

Two new thio/selenidogermanates [Ni 2 (μteta)(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 bridg-* Prof. Dr. X.-H. Yin Fax: +86-775-2622315

Ionothermal Access to Defined Oligomers of Supertetrahedral Selenido Germanate Clusters

“…The accessible void space is filled with the ionic liquid counterions. The Ge–(μ-Se) bond lengths (2.3674(12)–2.3771(11) Å) and Ge–Se terminal bond lengths (2.2604(13) Å) are within the range of reported values. ,,− …”

“…As shown in Figure , two T2 clusters are linked via sharing one μ-Se 2– ligand, while three terminal Se 2– ligands are retained per building unit. Again, Ge–(μ-Se) bond lengths (2.3296(19)–2.4127(21) Å) and Ge–Se terminal bond lengths (2.2388(21)–2.2640(30) Å) are close to the expected range. ,,− Another dimer of supertetrahedral clusters in (DBN-H + ) 6 [In 20 S 33 (DBN) 6 ] has recently been reported. , However, in this case, six of the terminal cluster positions were occupied by organic substituents, while the dimeric assembly in 2 has a purely inorganic composition.…”

The first examples of thiogermanate anion [GeS3(SH)]3−as a bridging ligand to a lanthanide complex

“…3 The organic template/structure-directing agents are commonly retained within the pore or cavity spaces. Recently, transition-metal complexes (TMCs) instead of tetraalkylammonium salts or nonchelating amines have been demonstrated to be useful as structure-directing agents in the thiogermanate system under solvothermal conditions and different anionic thiogermanates charge-balanced by TMCs have been synthesized, as exemplified by [TM(dap) 3 ] 4 Ge 4 S 10 Cl 4 (TM = Co, Ni), 4 [Ni(teta) 2 ] 2 Ge 4 S 10 , 5 [TM(dien) 2 ] 2 (H 2 dien)Ge 2 S 6 (TM = Co, Ni), 5,6 [Ni 2 (μ-teta)(teta) 2 ]Ge 4 S 10 •H 2 O, 6,7 [TM(en) 3 ] 2 -Ge 2 S 6 (TM = Mn, Co, Ni), 6,8 9 Some thiogermanate anions can also be further bonded with unsaturated TMCs, forming new neutral thiogermanates, such as {[Mn(tren)] 2 (μ 2 -Ge 2 S 6 )} 8a and {[TM(tepa)] 2 (μ 2 -Ge 2 S 6 )} (TM = Mn, Ni). 8a However, thiogermanates with lanthanide-containing counter cations have been less well explored under mild solvothermal conditions.…”

Stepwise Conversion from GeO2 to [MGe4S10]n3n– (M = Cu, Ag) Polymer via Isolatable [Ge2S6]4– and [Ge4S10]4– Anions by Virtue of Templating Technique

“…The [Ge 4 S 10 ] 4– adamantane-like anion is generated by the condensation of four {GeS 4 } tetrahedra through corner sharing. The Ge–S t bond lengths (2.1406(17)–2.1436(9) Å) are shorter than the Ge–S b bond lengths (2.2238(9)–2.2364(10) Å), suggesting the terminal S atoms are not protonated. , Comparison of the geometric data with those reported in literature (as listed in Table S2) shows no pronounced difference. ,− The slight deviation of the S–Ge–S bond angles (107.05(4)–111.66(5)°) from ideal 109.5° suggests a more moderate distortion of the {GeS 4 } tetrahedra compared to those in 1 and 1′ .…”