Across the Dimensions: A Three‐Component Self‐Assembly of Pentaphosphaferrocene‐based Coordination Polymers

Pentaphosphaferrocenes [CpRFe(η5‐P5)] (Cp*=η5‐C5Me5) (A), Cp’’=η5‐C5H3tBu2‐1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF6. Adding rigid aromatic dinitriles ortho/meta/para‐(NC)2C6H4 in a one‐pot reaction between [CpRFe(η5‐P5)] and AgSbF6 leads to various coordination polymers (CPs) by a three‐component self‐assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC)2C6H4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single‐crystal X‐ray diffraction. Coordination polymers: The combination of the rigid, aromatic dinitrile isomers ortho/meta/para‐(NC)2C6H4, the pentaphosphaferrocenes [CpRFe(η5‐P5)] (CpR=Cp*, Cp’’; Cp*=η5‐C5Me5; Cp’’=η5‐C5H3tBu2‐1,3) with different steric demands and a silver salt with a non‐coordinating anion SbF6− gives a unique view into how those building blocks can influence a three‐component self‐assembly system giving rise to various 1D/2D/3D‐coordination polymers.