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Abstract
The ternary system Ln/Sb/Se was investigated in a diethylenetriamine (dien) solvent under solvothermal conditions and two types of neutral lanthanide(III)–selenidoantimonate complexes [Ln(dien)2(μ-η1,η2-SbSe4)]n (Ln = Pr(1), Nd(2)) and [Ln(dien)2(η2-SbSe4)] (Ln = Sm(3), Gd(4)) were prepared. The lanthanide ions form [Ln(dien)2]3+ cations with two dien chelating ligands. In 1 and 2, is a tridentate μ-η1,η2-SbSe4 bridging ligand to connect [Ln(dien)2]3+ into one-dimensional coordination polymers [Ln(dien)2(μ-η1,η2-SbSe4)]n; it coordinates to [Sm(dien)2]3+ and [Gd(dien)2]3+ as a η2-SbSe4 bidentate chelating ligand, forming 3 and 4. Ln3+ in 1–2 and 3–4 are nine- and eight-coordinate environments, forming distorted monocapped square antiprisms and bicapped trigonal prisms, respectively. The different coordination modes of
between 1–2 and 3–4 are related to size of Ln3+. Complexes 1–4 exhibit semiconducting properties with band gaps of 2.08–2.28 eV.
Acknowledgments
This work was supported by the National Natural Science Foundation of P.R. China (No. 20771077, 21171123) and the Priority Academic Program Development of Jiangsu Higher Education Institutions.