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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. [ABSTRACT FROM AUTHOR]

Four new quaternary chalcogenides, Ba4AgGaS6 ( 1), Ba4AgGaSe6 ( 2), Ba4CuInS6 ( 3), and Ba4AgInS6 ( 4), were synthesized by solid-state reactions and their structures were characterized through single-crystal X-ray diffraction. In spite of their similar chemical compositions, the flexible arrangement between the transition metals and the triel atoms leads to subtle differences in their polyanion structures. All structures feature similar [MTrQ6]8− 1D polyanionic chains (M=Cu, Ag; Tr=Ga, In; Q=S, Se), which are constructed from corner-sharing MQ4 or TrQ4 tetrahedra. However, the transition metals and triels are mixed in 1, 2, and 3, but they occupy independent crystallographic sites in 4. As a result, compounds 1- 3 belong to the known Ba2CoS3 ( Pnma No. 62) or Ba2MnS3 ( Pnma No. 62) class, whereas 4 crystallizes in its own structural type within the monoclinic P21/ c (No. 14) space group. The structural relationship among these new phases was also studied with the aid of DFT calculations and related optical properties are presented as well. [ABSTRACT FROM AUTHOR]

Ba4AgGaS6 (I), Ba4AgGaSe6 (II), Ba4CuInS6 (III), and Ba4AgInS6 (IV) are prepared by solid-state reactions of the elements and/or binary chalcogenides (fused silica tube under Ar, 850-960 °C, 3-7 d). [ABSTRACT FROM AUTHOR]