A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscope (EPR). laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The fluorous-phase partitioning method (or liquid-liquid extraction). successfully applied for the first time in fullerene chemistry. aided by multi-stage recycling high performance liquid chromatography (HPLC) resulted in their isolation in isomer-free form. The present study opens the way to organic transformations of fullerene-based materials as a powerful separation technique. (C) 2002 Elsevier Science B.V. All rights reserved.