Synthesis and Structure of Multicomponent Crystals of Fullerenes and Metal Tetraarylporphyrins

The preparation of fullerene complexes with metal tetraarylporphyrins in the presence of excess ferrocene (Cp2Fe) results in the formation of new solvent-free and multicomponent molecular crystals. New isomorphous complexes of C60 with PyZnTPP (ZnTPP ≡ zinc 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) and PyCoTPP (CoTPP ≡ cobalt(II) 5,10,15,20-tetraphenyl-21H,23H-porphyrinate) containing Cp2Fe and the isostructural C70 complex with PyZnTPP have been prepared. The crystal structures of the new layered C60 complexes CoTMPP·C60 (obtained in the presence of Cp2Fe) and CoTMPP·2C60·3C7H8 (obtained in the absence of Cp2Fe) have been described (CoTMPP ≡ cobalt(II) 5,10,15,20-tetrakis(p-methoxyphenyl)-21H,23H-porphyrinate). Cobalt atoms of the PyCoTPP and CoTMPP molecules are weakly coordinated to C60 with Co···C(C60) distances in the 2.64−2.82 Å range, whereas zinc atoms of PyZnTPP, as well as cobalt atoms of the CoTMPP molecules in the solvent-free phase, form only van der Waals contacts with fullerenes. Different packing arrangements in the crystals of fullerene−porphyrin complexes have been discussed.