Iodoargentates from clusters to 1D chains and 2D layers induced by solvated lanthanide complex cations: syntheses, crystal structures, and photoluminescence properties

Abstract

Organic hybrid lanthanide(III) iodoargentates [Ln(DMSO)₈]₄Ag₂₂I₃₄·2H₂O (Ln = La (1), Ce (2)), [Ln(DMSO)₈]Ag₇I₁₀ (Ln = Eu (3), Tb (4), Dy (5)), and [Yb(DMSO)₇]Ag₅I₈ (6) (DMSO = dimethyl sulphoxide) were synthesized by a diffusion method and structurally characterized. In 1 and 2, twenty AgI₄ tetrahedra and two AgI₃ triangles are connected via edge-sharing, forming the highly nuclear cluster [Ag₂₂I₃₄]¹²⁻. In 3–5, the 2D [Ag₇I₁₀³⁻]_n layer is constructed from Ag₁₀I₁₈ and Ag₂I₅ secondary building units via edge-sharing. The parallel packing of the [Ag₇I₁₀³⁻]_n layers generates channels with cross-sectional dimensions of 5.5 × 18.2 Ų, in which the [Ln(DMSO)₈]³⁺ counterions are trapped. In 6, three AgI₄ and two AgI₃ units are joined via corner- or edge-sharing to form the asymmetric structural unit Ag₅I₈. The Ag₅I₈ units are interconnected into a 1D [Ag₅I₈³⁻]_n chain via corner-sharing. The formation of [Ag₂₂I₃₄]¹²⁻, [Ag₇I₁₀³⁻]_n and [Ag₅I₈³⁻]_n anions indicates the different structure-directing effects of the Ln(III) ions across the lanthanide series. Compounds 3 and 4 display intense red and green luminescence at room temperature excited by 393 and 369 nm light, respectively.