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Dalton Trans. 2013 Aug 21;42(31):11155-62. doi: 10.1039/c3dt50858g.

The syntheses, structures and properties of three new lanthanoid thioarsenates: the only example of thioarsenate acting as a ligand to a lanthanide complex.

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College of Chemistry, Chongqing Normal University, Chongqing, 401331, PR China.


Three new lanthanoid thioarsenates [Eu(en)3(η²-AsS₄)] (1, en = ethylenediamine), [Er(teta)(en)(η²-AsS₄)] (2, teta = triethylenetetramine) and [La₂(tepa)₂(μ-η¹,η³-AsS₃)₂] (3, tepa = tetraethylenepentamine) have been solvothermally synthesized and structurally characterized. In compounds 1 and 2, the tetrathioarsenate [AsS₄]³⁻ anions act as η²-AsS₄ chelating ligands to the lanthanide complexes [Eu(en)₃]³⁺/[Er(teta)(en)]³⁺, leading to neutral molecules [Eu(en)₃(η²-AsS₄)]/[Er(teta)(en)(η²-AsS₄)], whereas the [AsS₃]³⁻ anion in compound 3 acts as a μ-η¹,η³-AsS₃ tetradentate bridging ligand to link [La(tepa)]³⁺ ions into neutral centrosymmetric [La₂(tepa)₂(μ-η¹,η³-AsS₃)₂] moieties, where a new coordination mode of μ-η¹,η³-AsS₃ is observed for the [AsS₃]³⁻ ligand. Compounds 1-3 are the only examples of solvothermally synthesized thioarsenates where the [AsS₄]³⁻/[AsS₃]³⁻ anions act as ligands in the lanthanide complex. Compound 1 exhibits a fluorescence emission at room temperature. Density functional theory calculations for compounds 2 and 3 also have been performed, and the absorption edges of compounds 1-3 have been investigated by UV-vis spectroscopy.


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