Structural Requirements for Producing Solvent-Free Room Temperature Liquid Fullerenes

A new class of solvent-free room temperature liquid fullerenes was synthesized by attaching a single substituent of 1,3,5-tris­(alkyloxy)­benzene unit to C₆₀ or C₇₀ under the Prato conditions. Although the C₆₀ monoadducts were single components after chromatographic purification, the C₇₀ monoadducts were isomeric mixtures due to the prolate spheroidal π-chromophore. The alkyl chain length of the substituents significantly affected both melting points and rheological behavior of the fullerene derivatives. When the alkyl chains were short, the intermolecular π–π interactions of adjacent fullerene cores led to a melting point higher than room temperature. In contrast, in the case of exceedingly long alkyl chains, such as eicosyl (−C₂₀H₄₁) and docosanyl (−C₂₂H₄₅) groups, the van der Waals interactions among neighboring alkyl chains became dominant. Accordingly, only medium alkyl chain lengths could provide solvent-free fluidic fullerenes with low melting points. The rheological measurements of the liquid fullerenes at 25 °C revealed their unique liquid characteristics; molecular-level friction (or viscosity) and nanometer-scale clustering were noticed. It is generally thought that alkyl chains serve as a stabilizer of the fullerene core units. Thus, a longer chain or higher plasticity of the stabilizers would promote the disturbance of the core–core interactions. It was indeed shown that longer alkyl chains resulted in a lower fluid viscosity. It was also found that metastable solid phases were produced by the noticeable van der Waals interaction between the long alkyl chains especially when a symmetric C₆₀ core was adopted. This interesting finding enabled the comparison of electrochemical activities of the C₆₀ unit between the solvent-free liquid and metastable solid form, which revealed a superior electrochemical activity in the liquid state.