Confining the spin between two metal atoms within the carbon cage: redox-active metal-metal bonds in dimetallofullerenes and their stable cation radicals.

Lanthanide-lanthanide bonds are exceptionally rare, and dimetallofullerenes provide a unique possibility to stabilize and study these unusual bonding patterns. The presence of metal-metal bonds and consequences thereof for the electronic properties of M@C (M = Sc, Er, Lu) are addressed by electrochemistry, electron paramagnetic resonance, SQUID magnetometry and other spectroscopic techniques. A simplified non-chromatographic separation procedure is developed for the isolation of Er@C (C(6) and C(8) cage isomers) and Sc@C (C(8) isomer) from fullerene mixtures. Sulfide clusterfullerenes ErS@C with C(6) and C(8) fullerene cages are synthesized for the first time. The metal-metal bonding orbital of the spd hybrid character in M@C is shown to be the highest occupied molecular orbital, which undergoes reversible single-electron oxidation with a metal-dependent oxidation potential. Sulfide clusterfullerenes with a fullerene-based HOMO have more positive oxidation potentials. The metal-based oxidation of Sc@C-C is confirmed by the EPR spectrum of the cation radical [Sc@C-C] generated by chemical oxidation in solution. The spectrum exhibits an exceptionally large a(Sc) hyperfine coupling constant of 199.2 G, indicating a substantial 4s contribution to the metal-metal bonding orbital. The cationic salt [Er@C-C]SbCl is prepared, and its magnetization behavior is compared to that of pristine Er@C-C and ErS@C-C. The formation of the single-electron Er-Er bond in the cation dramatically changes the coupling between magnetic moments of Er ions.