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

A series of new hybrid chalcogenogermanates [Mn(en)GeS] (1, en = ethylenediamine), [Mn(dap)GeS] (2, dap = 1,2-diaminopropane), [Hdien][MnGeS] (3, dien = diethylenetriamine), [V(en)(ea)][GeSe] (4, Hea = ethanolamine), [V(teta)(ea)][GeSe] (5, teta = triethylenetetramine) and [V(en)(μ-O)][GeSe] (6) were solvothermally synthesized and structurally characterized. Both 1 and 2 contain dimeric [GeS] anions and [Mn(en)]/[Mn(dap)] complex cations, which are interconnected to generate 1-D neutral chain-like structures [Mn(en)GeS] and [Mn(dap)GeS], respectively. 3 consists of a protonated Hdien cation and a 1-D straight chain built from [MnS] and [GeS] 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 [GeSe] anions constructed by two [GeSe] tetrahedra sharing a common edge and discrete complex cations [V(en)(ea)]/[V(teta)(ea)]. 6 is composed of a [GeSe] anion and dinuclear complex cation [V(en)(μ-O)] 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.