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

Abstract

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.