An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers

Pentaphosphaferrocenes [CpR Fe(η5 -P5 )] (1) and CuI halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF3 SO3 ) for the construction of the novel 2D polymer [{Cp*Fe(μ4 ,η5:1:1:1 -P5 )}{Cu(CF3 SO3 )}]n (2) and the unprecedented nanosphere (CH2 Cl2 )1.4 @[{CpBn Fe(η5 -P5 )}12 {Cu(CF3 SO3 )}19.6 ] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron. Combinatorics was used to interpret the average disordered structure of the supramolecules. In this case, only two pairs of enantiomers with D5 and D2 symmetry are possible for bidentate bridging coordination of the triflate ligands. DFT calculations showed that differences in the energies of the isomers are negligible. The benzyl ligands enhance the solubility of 3, enabling NMR-spectroscopic and mass-spectrometric investigations.