Penta(pyrenyl)[60]fullerenes: Pyrene–Pyrene and [60]Fullerene–Pyrene Interactions in the Crystal and in Solution

A new type of fullerene–pyrene hybrid molecule, C60Ar5R [Ar=1‐pyrenyl, 4‐(1‐pyrenyl)C6H4, 4‐{(1‐pyrenyl)CO2}C6H4, and 4‐{(1‐pyrenyl)(CH2)3CO2}C6H4; R=H and Me] was synthesized by a regioselective penta‐addition reaction using organocopper reagents. The compounds were investigated using electrochemical measurements, DFT calculations, single‐crystal X‐ray structural analysis, and spectroscopic and fluorescence measurements. Intramolecular and intermolecular fullerene–pyrene and pyrene–pyrene interactions were characterized in the crystals. Fluorescence measurements in dilute solutions suggested the presence of intramolecular fullerene–pyrene and pyrene–pyrene interactions. Close encounters of the π kind: A new type of fullerene–pyrene hybrid molecule, C60Ar5R (Ar=tethered 1‐pyrenyl derivative; R=H and Me), was synthesized by a regioselective penta‐addition reaction using organocopper reagents. Intramolecular and intermolecular fullerene–pyrene and pyrene–pyrene interactions were characterized in the crystal and in solution using electrochemical measurements, DFT calculations, single‐crystal X‐ray structural analyses, and fluorescence measurements.