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.