Solvothermal synthesis and optical property of novel lanthanide(III) coordination polymers involving inorganic tridentate μ-η1,η2-SbS4 S-donor ligand

Two novel inorganic-organic hybrid lanthanide thioantimonates [Ln(dien)2(μ-η1,η2-SbS4)]∞ (Ln = La(1), Ce(2)) were synthesized by reaction of LaCl3 (or CeCl3), Sb and S in dien (dien = diethylenetriamine) under solvothermal conditions. In 1 and 2, the [SbS4]3− anions act as tridentate μ-η1,η2-SbS4 bridging ligands to connect [Ln(dien)2]3+ cations into one-dimensional neutral coordination polymers [Ln(dien)2(μ-η1,η2-SbS4)]∞, in which a new coordination mode of μ-η1,η2-SbS4 is observed for the [SbS4]3− ligand. The Ln3+ ions lie in nine-coordinated polyhedra of LnN6S3, which can be described as distorted monocapped square antiprisms. The syntheses of 1 and 2 show that the soft base S-donor [SbS4]3− ligand can coordinate to hard Lewis acidic lanthanide metals in the presence of amino chelating ligands of dien. The lanthanide selenidoarsenates 1 and 2 exhibit semiconducting properties with Eg between 3.81 and 2.57 eV.