Mono-reduced Corannulene: To Couple and Not to Couple in One Crystal

One-electron reduction of corannulene, C₂₀ H₁₀ , with Li metal in diglyme resulted in crystallization of [{Li⁺ (diglyme)₂ }₄ (C₂₀ H₁₀ ^.- )₂ (C₂₀ H₁₀ -C₂₀ H₁₀ )^2- ] (1), as revealed by single-crystal X-ray diffraction. This hybrid product contains two corannulene monoanion-radicals along with a dianionic dimer, crystallized with four Li⁺ ions wrapped by diglyme molecules. The dimeric (C₂₀ H₁₀ -C₂₀ H₁₀ )^2- anion provides the first crystallographically confirmed example of spontaneous radical dimerization for C₂₀ H₁₀ ^.- . The C-C bond length between the two C₂₀ H₁₀ ^.- bowls of 1.588(5) Å is consistent with the single σ-bond character of the linker. The trans-disposition of two bowls in the centrosymmetric (C₂₀ H₁₀ -C₂₀ H₁₀ )^2- dimer is observed with the torsion angle around the central C-C bond of 180°. Comprehensive theoretical analysis of formation/decomposition processes of the dimeric dianion has been carried out in order to evaluate the nature of bonding and energetics of the C₂₀ H₁₀ ^.- coupling. It is found that such σ-bonded dimers are thermodynamically unstable due to large preparation energy and repulsive Pauli component of the bonding, but kinetically persistent due to a high energy barrier provided by the existing spin-crossing point.