[Mn₂Ga₄Sn₄S₂₀]⁸⁻ T3 supertetrahedral nanocluster directed by a series of transition metal complexes

With different transition metal (TM) complexes as structure directing agents or building units, three new multinary chalcognidometalates based on T3 supertetrahedral nanocluster of [Mn₂Ga₄Sn₄S₂₀]⁸⁻ have been solvothermally synthesized and structurally characterized. In compound Mn₂Ga₄Sn₄S₂₀[Mn₂(en)₅]₂·4H₂O (1, en = ethylenediamine), the neighboring [Mn₂Ga₄Sn₄S₂₀]⁸⁻ cores were bridged by two pairs of [Mn₂(en)₅]⁴⁺ complex cations via Mn–S bonds to form one-dimensional (1D) neutral chains. Compound Mn₂Ga₄Sn₄S₂₀[Mn(dien)₂]₄·2H₂O (2, dien = diethylenetriamine) contained discrete [Mn₂Ga₄Sn₄S₂₀]⁸⁻ cores separated by [Mn(dien)₂]²⁺ cations. In compound Mn₂Ga₄Sn₄S₂₀[Mn(teta)]₄ (3, teta = triethylenetetramine), each [Mn₂Ga₄Sn₄S₂₀]⁸⁻ core was covalently attached by four [Mn(teta)]²⁺ complexes via terminal Mn–S bonds to form a neutral isolated cluster. The photocatalytic experiments indicate that compound 1 was able to degrade rhodamine B (RhB) and crystal violet (CV) under visible irradiation. Furthermore, the luminescence properties and thermal stabilities of the title compounds, as well as the second-order nonlinear optical property of 3 were also studied.