A Nano-sized Supramolecule Beyond the Fullerene Topology**

The reaction of [Cp(Bn) Fe(η(5) -P5 )] (1) (Cp(Bn) =η(5) -C5 (CH2 Ph)5 ) with CuI selectively yields a novel spherical supramolecule (CH2 Cl2 )3.4 @[(Cp(Bn) FeP5 )12 {CuI}54 (MeCN)1.46 ] (2) showing a linkage of the scaffold atoms which is beyond the Fullerene topology. Its extended CuI framework reveals an outer diameter of 3.7 nm-a size that has not been reached before using five-fold symmetric building blocks. Furthermore, 2 shows a remarkable solubility in CH2 Cl2 , and NMR spectroscopy reveals that the scaffold of the supramolecule remains intact in solution. In addition, a novel 2D polymer [{Cp(Bn) Fe(η(5) -P5 )}2 {Cu6 (μ-I)2 (μ3 -I)4 }]n (3) with an uncommon structural motif was isolated. Its formation can be avoided by using a large excess of CuI in the reaction with 1.