Novel Two- and Three-Dimensional Organometallic–Organic Hybrid Materials Based on Polyphosphorus Complexes

The reaction of the silver salt Ag­[Al­{OC­(CF₃)₃}₄] (<b>1</b>) with the P₂ ligand complex [Cp₂Mo₂(CO)₄(η²-P₂)] (<b>2</b>) and the organic ditopic linker <i>trans</i>-1,2-di­(pyridine-4-yl)­ethene (<i>dpe</i>) results in the formation of four novel organometallic–organic hybrid compounds. Depending on the reaction conditions, the two-dimensional networks [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}­(μ,η^1:1-C₁₂H₁₀N₂)­Ag]_<i>n</i>[Al­{OC­(CF₃)₃}₄]_<i>n</i>·0.075<i>n</i>CH₂Cl₂·1.425<i>n</i>C₆H₆ (<b>3</b>) and [{Cp₂Mo₂(CO)₄(μ₃,η^2:2:2-P₂)}₂(μ,η^1:1-C₁₂H₁₀N₂)₃Ag₂]_<i>n</i>[Al­{OC­(CF₃)₃}₄]_2<i>n</i>·2<i>n</i>C₇H₈ (<b>4</b>) are accessible. The latter shows a two-dimensional (2D) → 2D interpenetration structure. Furthermore, the formation of a unique three-dimensional polymer [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}­(μ,η^1:1-C₁₂H₁₀N₂)­Ag]_<i>n</i>[Al­{OC­(CF₃)₃}₄]_<i>n</i>·0.3<i>n</i>CH₂Cl₂ (<b>5b</b>) together with another 2D polymer [{Cp₂Mo₂(CO)₄(μ₄,η^1:1:2:2-P₂)}­(μ,η^1:1-C₁₂H₁₀N₂)₃Ag₂]_<i>n</i>[Al­{OC­(CF₃)₃}₄]_2<i>n</i>·0.75CH₂Cl₂·0.5C₇H₈ (<b>5a</b>) was observed. In three of these polymers, unprecedented organometallic nodes were realized including one, two, or even four silver cations. All products were characterized by X-ray structural analysis and classified by the structural characteristics in three different network topologies