A series of new vanadium(iii) chalcogenido-antimonates: an unusual seven-coordinate nitro-selenidovanadium(iii) complex.

Abstract

A series of new vanadium(iii) chalcogenidoantimonates [VIII(dap)2SbQ3] (Q = S (1), Se (2); dap = 1,2-diaminopropane), [H2dien][VIII2(en)2(dien)2(μ2-O)][SbSe4]2 (3, en = ethylenediamine; dien = diethylenetriamine) and [VIII(dien)2SbSe4] (4) have been solvothermally synthesized and structurally characterized. Both 1 and 2 contain neutral vanadium(iii)-centered complexes [VIII(dap)2SbQ3], where the [SbQ3]3- anion acts as a chelating ligand to complex [VIII(dap)2]3+, but they exhibit different molecular conformations. 3 consists of selenidoantimonate anions [SbSe4]3-, the protonated H2dien2+ cation, and the dinuclear complex [VIII2(en)2(dien)2(μ2-O)]4+ based on two [VIII(en)(dien)]3+ units bridged by one μ2-O group. 4 contains neutral [VIII(dien)2SbSe4] moieties with seven coordinated vanadium centres, which offers a rare example of high coordination of a nitro-selenidovanadium(iii) complex, mainly because the vanadium(iii) ion has a regular octahedral configuration based on the structures in the solid state. The optical, magnetic and photoelectronic properties of all compounds have been investigated, and the density functional theory calculation of 4 has also been studied.