A series of new hybrid chalcogenogermanates: the rare examples of chalcogenogermanates combined with trivalent vanadium complexes.

A series of new hybrid chalcogenogermanates [Mn2(en)4Ge2S6]n (1, en = ethylenediamine), [Mn2(dap)4Ge2S6]n (2, dap = 1,2-diaminopropane), [H2dien]n[MnGeS4]n (3, dien = diethylenetriamine), [V(en)2(ea)]2[Ge2Se6] (4, Hea = ethanolamine), [V(teta)(ea)]2[Ge2Se6] (5, teta = triethylenetetramine) and [V2(en)6(μ-O)][Ge2Se6] (6) were solvothermally synthesized and structurally characterized. Both 1 and 2 contain dimeric [Ge2S6]4- anions and [Mn(en)2]2+/[Mn(dap)2]2+ complex cations, which are interconnected to generate 1-D neutral chain-like structures [Mn2(en)4Ge2S6]n and [Mn2(dap)4Ge2S6]n, respectively. 3 consists of a protonated H2dien2+ cation and a 1-D straight chain built from [MnS4] and [GeS4] tetrahedra sharing opposite edges, and is the only example of a chelating amine uncoordinated to a transition metal ion. Both 4 and 5 consist of [Ge2Se6]4- anions constructed by two [GeSe4] tetrahedra sharing a common edge and discrete complex cations [V(en)2(ea)]2+/[V(teta)(ea)]2+. 6 is composed of a [Ge2Se6]4- anion and dinuclear complex cation [V2(en)6(μ-O)]4+ containing an en molecule as a rare monodentate ligand. Although some selenidogermanates with transition metal complexes have been successfully prepared, no selenidogermanates with trivalent vanadium complexes have been documented. Therefore, 4-6 offer the first examples of selenidogermanates with trivalent vanadium complexes under solvothermal conditions. Their optical and photocurrent response properties were studied.