Metal‐Deficient Supramolecule Based on a Fivefold‐Symmetric Building Block

An unprecedented cationic supramolecule [(Cp′′Fe(η(5)‐P(5)))(12){CuNCMe}(8)](8+) 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF(3))(3)}(4)](−) for the first time and characterized by X‐ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal‐deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal‐deficient pentaphosphaferrocene‐based supramolecules [{Cp(R)Fe(η(5)‐P(5))}(12)(CuX)(20−n)]. The 12 vacant metal sites between the cyclo‐P(5) rings, the largest number attained to date, make this compound a facile precursor for potential inner and outer modifications of the core as well as for functionalization via the substitution of labile acetonitrile ligands.