A series of new lanthanoid thioantimonates [Ln(teta)2]SbS4 [teta = triethylenetetramine; Ln = Eu (1), Gd (2), Er (3)], {[Ln(tepa)]2[μ2-SbIIIS3](μ2-OH)}2{[Ln(tepa)]2(μ2-OH)2(SbVS4)2}Cl2 [tepa = tetraethylene-pentamine; Ln = Y(4), Eu(5), Er(6)], and [Gd2(tepa)2(μ2-OH)2(μ2-SbS4)]Cl·0.25H2O (7) were synthesized via reactions of Sb, S and LnCl3 in teta or tepa under solvothermal conditions and were structurally characterized. Compounds 1–3 consist of isolated [Ln(teta)4]3+ cations and tetrahedral [SbS4]3− anions. Compounds 4–6 contain heterometallic mixed amino-thiocluster cations {[Ln(tepa)]2[μ2-SbS3](μ2-OH)}2+, heterometallic anions {[Ln2(tepa)2(μ2-OH)2](SbS4)2}2− and free Cl− ions, which provide a rare example of the coexistence of noncondensed pyramidal [SbIIIS3]3− and tetrahedral [SbVS4]3− anions in a single thioantimonate. 7 consists of a 1-D polymeric cation [Gd2(tepa)2(μ2-OH)2(μ2-SbS4)]+, constructed through the linkage of asymmetric dinuclear gadolinium complex [Gd2(tepa)2(μ2-OH)2]4+ cations, tetrahedral [SbVS4]3− anions and a Cl− ion and water molecule, which represents a rare example of organic-decorated cationic lanthanoid thioantimonate chains based on asymmetric dinuclear lanthanide complexes. The present compounds exhibit semiconducting properties with absorption band edges between 2.00 and 3.03 eV.
