Experimental observation of C60 LUMO splitting in the C602− dianions due to the Jahn–Teller effect. Comparison with the C60˙− radical anions

New fullerene salts (TMP+)2·(C602−)·(C6H4Cl2)2 (1), {DB-18-crown-6·[Na+]·(C6H5CN)2}2·(C602−)·C6H5CN·C6H4Cl2 (2), {cryptand[2,2,2]·(Na+)}2·(C602−) (3) and (PPN+)2·(C602−)·(C6H4Cl2)2 (4) were obtained as single crystals. Their crystal structures were solved and their optical and magnetic properties were analyzed. The spectra of the salts in the IR and UV-visible-NIR ranges indicate the formation of C602− dianions in 1–4. These salts show similar behavior in EPR measurements, explained by the diamagnetic ground state of the C602− dianions and the thermal population of the excited triplet state, which is separated by an energy gap of 487–540 cm−1. The magnetic susceptibility of 4 also increased above 130 K due to the population of the excited triplet state. The observed splitting of the C60 LUMO is attributed to the Jahn–Teller (JT) effect. We analyzed the splitting by an extended Hückel method using the single-crystal structural data for the compounds containing neutral, mono- and dianions of C60. The splitting of the initially triply degenerated C60 LUMO produces three molecular orbitals. The gap between the lowest and highest orbitals is very small in neutral C60 (128–140 cm−1), it increases in C60˙− (500–710 cm−1) and increases further in C602− (1080–1670 cm−1). It was found that the splitting of the C60 LUMO is realized in different ways for the mono- and dianions. The ground and first excited state are separated in C60˙− by a small gap of 55–180 cm−1 only. This gap is noticeably larger in the C602− dianions and falls into the 760–1390 cm−1 range.