Polymeric templates and solvent effects: syntheses and properties of polymeric iodoargentates containing solvated [Mn(4,4′-bpy)]2+ cations

Abstract

Four new polymeric iodoargentates were prepared by the reactions of AgI and KI templated by solvated [Mn(4,4′-bpy)]²⁺ complex cation in different mixed solvents. The reaction in DMF/H₂O, DMSO/H₂O, and DMF/DMSO/H₂O (DMF = N,N’-dimethylformamide; DMSO = dimethylsulfoxide) produced [Mn(4,4′-bpy)(DMF)₃(H₂O)]Ag₅I₇·4,4′-bpy (1), [Mn(4,4′-bpy)(DMSO)₄]₂Ag₁₁I₁₅ (2), [Mn(4,4′-bpy)₂(DMSO)₂(H₂O)₂]Ag₁₀I₁₂·2DMSO·2H₂O (3), and [Mn₂(4,4′-bpy)₂(DMF)₅(DMSO)₂(H₂O)]Ag₁₀I₁₄·2DMF (4) (4,4′-bpy = bipyridine), respectively. In 1, four AgI₄ units are joined by sharing common edges forming a Ag₄I₉ fragment. The Ag₄I₉ fragments are connected into a 1-D [Ag₅I₇²⁻]_n polymeric anion by a AgI₄ unit. In 2, six AgI₄ units share common edges to form [Ag₆I₁₂]_n chain-like subunits. Two [Ag₆I₁₂]_n subunits are joined by μ-I bridges, forming a novel ladder-shaped [Ag₁₁I₁₅⁴⁻]_n polymeric anion. The [Ag₁₀I₁₂²⁻]_n in 3 is composed of a circular Ag₅I₁₂ subunit via sharing five terminal iodine atoms. Two Ag₄I₉ and one Ag₂I₄ fragments are interjoined via sharing a common face to form the 1-D [Ag₁₀I₁₄⁴⁻]_n anion in 4. Compounds 1, 2 and 4 are the first examples of iodoargentates containing polymeric counter cations. The stronger Ag⋯Ag interactions in the [Ag₁₁I₁₅⁴⁻]_n and [Ag₁₀I₁₄⁴⁻]_n anions cause red-shift in the luminescent spectra of compounds 2 and 4, compared with those of 1 and 3.