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] (1) with the P2 ligand complex [Cp2Mo2(CO)4(η(2)-P2)] (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 [{Cp2Mo2(CO)4(μ4,η(1:1:2:2)-P2)}(μ,η(1:1)-C12H10N2)Ag]n[Al{OC(CF3)3}4]n·0.075nCH2Cl2·1.425nC6H6 (3) and [{Cp2Mo2(CO)4(μ3,η(2:2:2)-P2)}2(μ,η(1:1)-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·2nC7H8 (4) 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]n[Al{OC(CF3)3}4]n·0.3nCH2Cl2 (5b) together with another 2D polymer [{Cp2Mo2(CO)4(μ4,η(1:1:2:2)-P2)}(μ,η(1:1)-C12H10N2)3Ag2]n[Al{OC(CF3)3}4]2n·0.75CH2Cl2·0.5C7H8 (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.