New Selenidogermanates with Transition-Metal Complexes as Counterions: Solvothermal Synthesis, Crystal Structures, and Properties of [Mn(en)3]2Ge2Se6 and [Fe(dien)2]2Ge2Se6

Solvothermal Syntheses and Characterization of New Transition Metal Chalcogenidogermanates [{Co(tepa)}2(μ‐Ge2S6)] and [{M(tepa)}2(μ‐Ge2Se6)] (M = Mn, Fe) (tepa = Tetraethylenepentamine)

“…The S–Ge–S angles of μ‐Ge 2 S 6 in 1 vary in a wide range of 109.90(5)–115.48(5)° (Table 2), whereas the corresponding angles vary in a narrow range of 110.75(4)–113.26(4)° for the free [Ge 2 S 6 ] 4– anions in the compounds [Mn(en) 3 ] 2 Ge 2 S 6 and [Ni(en) 3 ] 2 Ge 2 S 6 21. The same evolution of Se–Ge–Se angles is observed between μ‐Ge 2 Se 6 ligands in 2 and 3 and free [Ge 2 Se 6 ] 4– anions in [Mn(en) 3 ] 2 Ge 2 Se 6 and [Fe(dien) 2 ] 2 Ge 2 Se 6 22. The structural parameters of the Ge 2 E 2 squares in μ‐Ge 2 E 6 units are related with the chalcogen atoms.…”

“…Ethylene polyamine serves not only as reaction solvent, but also as chelating ligand to coordinate to TMs n + forming a complex cation, which acts as space filler and/or charge compensating ion in chalcogenidometalatecompounds. The ethylene polyamines ethylenediamine (en) and diethylenetriamine (dien) were widely investigated in the solvothermal syntheses of chalcogenidostannates and chalcogenidogermanates, and the compounds [M(en) 3 ] 2 Sn 2 S 6 (M = Mn, Co, Zn, Ni) [16, 17], [Ni(dien) 2 ] 2 Sn 2 S 6 17, [M(en) 3 ] 2 Sn 2 Se 6 (M = Mn, Zn) 18, [M(en) 3 ] 2 Sn 2 Te 6 (M = Mn, Zn) [19, 20], [M(en) 3 ] 2 Ge 2 S 6 (M = Mn, Ni) 21, [Mn(en) 3 ] 2 Ge 2 Se 6 22, [Fe(dien) 2 ] 2 Ge 2 Se 6 22, and [Mn(dien) 2 ] 2 Ge 2 Se 7 23 were prepared in en and dien respectively. In these compounds, the TM 2+ complex cations and chalcogenidometalate anions are discreted.…”

Five dimeric thiogermanates with transition metal complexes of multidentate chelating amines: Syntheses, structures, magnetism and photoluminescence

“…Up to now, in the known hybrid chalcogenogermanates, the TMCs are generally used as discrete counter-cations [23][24][25], while the examples of chalcogenogermannates integrated with TMCs via TM-S/Se bonds are limited, such as {[Cr(en) 2 ](GeS 4 )} À , {[Cr(en)] 2 (GeSe 4 ) 2 } 2À [26], {[Mn(cyclam)] 2 (l-Ge 2 Se 7 )}ÁCH 3 OHÁ1.5H 2 O (cyclam = 1,4,8,11-tetraazacyclotetradecane) [27], {[Co(tepa)] 2 (l-Ge 2 S 6 )}, {[M(tepa)] 2 (lGe 2 Se 6 )} (M = Mn, Fe) [28]. Although it is known that the size, shape and charge of the TMC cations play a very important role in the construction of the inorganic main-group metal chalcogenide anions, a clear relationship between them still not observed and more compounds need to be synthesized for further understanding.…”

Mineralizer effect on the synthesis of two types of one-dimensional chains silver-selenogermanate and selenostannate

“…1, which is constructed by two GeSe 4 tetrahedral sharing a common edge to form a planar Ge 2 Se 2 square. In dimeric anion, bridging Ge1-Se1 bond [20], A 2 Ge 2 Se 6 (A = Na, K, Rb, Cs) [21][22][23][24].…”