The (13)C NMR spectra were measured for three isomers of Tm@C(82), which is one of the divalent metallofullerenes. The molecular symmetries were determined for each isomer: isomer I has C(s) symmetry, isomer II has C(2) symmetry, and isomer III has C(2v) symmetry. Moreover the cage structure of Tm@C(82)(III) was found to be C(82)(9). As a result, it was revealed that Tm@C(82)(III) has a cage identical to that of La@C(82), which is one of the trivalent metallofullerenes.

In this work, the cage structure of a family of europium metallofullerenes, Eu@C 74 and three isomers of Eu@C 82 , were investigated. The analogy of the electronic states of three isomers of Eu@C 82 with those of three isomers of Ca@C 82 was confirmed by UV-vis-near-IR absorption spectra. The symmetries C s , C 2 , and C 2V were assigned for three isomers of Eu@C 82 by comparing each corresponding isomer of Ca@C 82 . The D 3h cage structure of Eu@C 74 , which is expected only for the C 74 from the isolated pentagon rule, was also confirmed by comparing its photoabsorption spectrum with that of Ca@C 74 . Multifrequency electron paramagnetic resonance (EPR) spectroscopy was employed to determine the zero-field splitting (ZFS) parameters of the metallofullerenes, which are closely related to the surrounding cage structures. The experimental X-and W-band EPR spectra were completely reproduced by computer simulations based on a spin Hamiltonian considering the ZFS terms up to fourth order. The introduction of the fourth-order ZFS terms into the Hamiltonian resulted in a precise determination of the second-order ZFS terms. A nonvanishing rhombicity parameter E of Eu@C 74 demonstrated the reduction of the symmetry from D 3h to C 2V due to the positioning of Eu 2+ ion at the off-center of C 74 cage. Moreover, in this work, the semiphenomenological superposition-exchange model (SPEM) was invoked to examine a relationship between the molecular structures and ZFS parameters. All of the experimental ZFS parameters were satisfactory reproduced in terms of the SPEM, leading to confirmation of the molecular symmetries. The semiphenomenological analysis also enabled us to select the most appropriate cage for Eu@C 82 with C 2 symmetry from among three possible isomers.