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

[Image: see text] The reaction of the silver salt Ag[Al{OC(CF(3))(3)}(4)] (1) with the P(2) ligand complex [Cp(2)Mo(2)(CO)(4)(η(2)-P(2))] (2) and the organic ditopic linker trans-1,2-di(pyridine-4-yl)ethene (dpe) results in the formation of four novel organometallic–organic hybrid compounds. Depending on the reaction conditions, the two-dimensional networks [{Cp(2)Mo(2)(CO)(4)(μ(4),η(1:1:2:2)-P(2))}(μ,η(1:1)-C(12)H(10)N(2))Ag](n)[Al{OC(CF(3))(3)}(4)](n)·0.075nCH(2)Cl(2)·1.425nC(6)H(6) (3) and [{Cp(2)Mo(2)(CO)(4)(μ(3),η(2:2:2)-P(2))}(2)(μ,η(1:1)-C(12)H(10)N(2))(3)Ag(2)](n)[Al{OC(CF(3))(3)}(4)](2n)·2nC(7)H(8) (4) are accessible. The latter shows a two-dimensional (2D) → 2D interpenetration structure. Furthermore, the formation of a unique three-dimensional polymer [{Cp(2)Mo(2)(CO)(4)(μ(4),η(1:1:2:2)-P(2))}(μ,η(1:1)-C(12)H(10)N(2))Ag](n)[Al{OC(CF(3))(3)}(4)](n)·0.3nCH(2)Cl(2) (5b) together with another 2D polymer [{Cp(2)Mo(2)(CO)(4)(μ(4),η(1:1:2:2)-P(2))}(μ,η(1:1)-C(12)H(10)N(2))(3)Ag(2)](n)[Al{OC(CF(3))(3)}(4)](2n)·0.75CH(2)Cl(2)·0.5C(7)H(8) (5a) 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.