Linear Arrays of Interlocking Calixarenes in Controlling the Interplay of Fullerene C60 Molecules

p-Benzylcalix[6]arene, 1, and C60 form a fullerene rich inclusion complex in toluene, (C60)3(p-benzylcalix[6]arene)(toluene)4.25, 2, which has been structurally authenticated. The fullerene and toluene molecules shroud linear arrays of the calixarenes, which are dethreaded in the presence of methylene chloride to form an all carbon hcp polymorph of fullerene C60. The ease of dethreading relates to the mode of association of p-benzylcalix[6]arene within the molecular crystal consisting of interlocked calixarenes in linear arrays. Similar association has also been seen in the solid-state structure of p-benzylcalix[6]arene, 1, where one calixarene is associated with another through two modes, a frontal host–guest association involving inclusion of the pendent benzyl arms and back-to-back stacking arrangement.