Isolation and Monitoring of the Endohedral Metallofullerenes Y@C₈₂ and Sc₃@C₈₂: On-Line Chromatographic Separation with EPR Detection

The direct coupling of high-performance liquid chromatography (HPLC) with on-line electron paramagnetic resonance (EPR) detection is demonstrated for monitoring separations of endohedral metallofullerenes (M@C2n). The HPLC-EPR approach readily permits detection of the paramagnetic species, such as Y@C82 and Sc3@C82, in the presence of the dominant empty-cage fullerenes (C60, C70) and diamagnetic metallofullerenes (e.g., M2@C2n). The results indicate that on-line EPR provides a noninvasive, selective detector for HPLC metaliofullerene separations that is readily adaptable to airsensitive and/or labile compounds. Specifically, the “EPR-active” metallofullerenes, Y@C82 and Sc3@C82, are selectively monitored on-line for an initial separation of the metaliofullerene fraction from the dominant empty-cage fullerenes utilizing a combination of polystyrene columns. This preparative “cleanup” procedure is followed by HPLC-EPR separation and monitoring of Y@C82 and Sc3@C82 species using a selective tripodal π-acidic-phase column (Trident-Tri-DNP) for the final stages of isolation. © 1994, American Chemical Society. All rights reserved.