A methanofullerene derivative with an ammonium subunit () has been prepared and its ability to form a supramolecular complex with a porphyrin–crown ether conjugate evidenced by NMR, UV–vis, electrospray mass spectrometry (ES-MS) and luminescence experiments. Interestingly, in addition to the ammonium–crown ether recognition, intramolecular stacking of the fullerene moiety and the porphyrin subunit has been evidenced. Due to this ...