Abstract
Antiferromagnetic coupling of spins with spin frustration and fullerene dimerization are observed for (Ph3MeP+)(C60˙−) (left) and (Ph3MeP+)(C60˙−)·C6H5CN (right).
Highlights
The C60À radical anions should be closely packed in a crystal to show strong magnetic coupling of spins or metallic conductivity
Fullerene oxidized the VIVOPc(3À)À radical anions forming a violet solution of (Ph3MeP+)(C60À), whereas neutral VIVOPc, which is insoluble in pure o-dichlorobenzene, quantitatively precipitated from the solution
When C60 was reduced by fluorenone ketyl in C6H4Cl2 in the presence of Ph3MeP+, insoluble precipitates were formed, which was dissolved by adding C6H5CN
Summary
Since unpaired electrons are paired at the formation of the interfullerene C–C bonds in the dimers, the compounds transfer to the diamagnetic state and cannot show high conductivity. The cations and neutral molecules with appropriate shapes and sizes are required to provide promising physical properties of ionic fullerene compounds.[1,6,7,15,16] Fullerenes can be dimerized[17] or polymerized[2,3] by the [2+2] cycloaddition reaction. In this case, the additional electron is preserved on the singly occupied molecular orbital (SOMO) of C60 and the compound can either be metallic[2,3] or show strong magnetic coupling of spins.[17]. Dimerization of C60À is realized in 2 to form singly-bonded (C60À)[2] dimers and the reversible transition of the salt to the diamagnetic state
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