Origin of ferromagnetic exchange interactions in a fullerene–organic compound

Organic ferromagnets, which exhibit exchange interactions between unpaired electrons in π-orbitals, are rare1,2,3,4,5,6, and the origin of ferromagnetism in these compounds has so far remained unexplained. Tetrakis(dimethylamino)ethylene–fullerene[60] (TDAE–C60) shows a transition to a ferromagnetic state with fully saturated s = 1/2 molecular spins at the relatively high Curie temperature (for organic materials) of 16 K (ref. 4). It has been suggested7,8,9 that the orientations of the C60 molecules may be important for ferromagnetism in this material, but in the absence of structural data at low temperatures there has been little progress towards understanding these microscopic interactions. Here we report the results of a comparative structural study of two different magnetic forms of TDAE–C60 crystals at low temperatures, correlating the structural properties—in particular, the intermolecular orientations—with the magnetic properties. We find that both ferromagnetism and spin-glass-like ordering are possible in this material, and depend on the orientational state of C60 molecules. This resolves the apparent contradictions posed by different macroscopic measurements4,10,11,12,13,14, and opens the way to a microscopic understanding of π-electron ferromagnetic exchange interactions in organic materials.