Phthalocyanines (Pcs) are planar, two-dimensional aromatic macrocycles which possess outstanding electrical and optical properties that make them perfect building blocks for their incorporation into multifunctional materials. Similarly, the excellent electron-accepting property of C₆₀ fullerene renders this carbon nanostructure an ideal molecular partner for photo- and electroactive molecular systems such as Pcs.

Although several reports have appeared on the preparation of Pc-based, mono-functionalized fullerenes, not many examples have been reported concerning the double functionalization of C₆₀ fullerene by Pcs, which remains problematic due to the formation of a large number of regio- and/or stereoisomers.

Here, we report a novel example of controlled bisaddition over C₆₀ fullerene in which the occurrence of π-π supramolecular interactions between structurally-rigid, Pcs addends in solution led to the formation of a Pc₂-C₆₀ bisadduct triad in a regio- and stereocontrolled fashion. In the Pc₂-C₆₀ triad, the two Pc units are interacting through intramolecular π-stacking interactions, as demonstrated by several techniques (i.e., DABCO titration experiments, ground- and excited state photophysical studies, HPLC analysis, electrochemical studies, etc.).