Cocrystallites consisting of metal macrocycles with fullerenes

The cocrystallites that contain C-60, C-70 and endohedral metallofullerenes with metal complexes of macrocycles are reviewed. Metal complexes of porphyrin cocrystallites with fullerenes form solids with remarkably close contact between the curved 7 surface of a fullerene and the planar pi surface of a porphyrin, without the need for matching convex with concave surfaces. The structures of metal octaethylporphyrins (oeps) in C-60.Pd(II)(oep).1.5C(6)H(6), C-60.Cu(II)(oep).2C(6)H(6), C-60.Ag(II)(oep).2C(6)H(6) and C-60.2Ni(II)(oep).2C(6)H(5)Cl reveal the remarkable anti-formed oep configurations, with the four ethyl groups of the metal oep portions lying on both the same and the opposite sides of the porphyrin plane toward the C-60. On the other hand, syn-formed metal oeps are observed in the many cases of metal oep compounds, suggesting that there is a face-to-face interaction between two adjacent oep planes. A new cocrystallite which exhibits a strong intermolecular interaction between fullerene C-60 and the Co(tbp) is also reviewed, where tbp denotes a dianion of tetra(bis-tert-butylphenyl)porphyrin. The intermolecular interactions of the anti- and syn-formed metal oeps in the cocrystallites containing fullerenes are also described by DV-Xalpha molecular orbital calculation. (C) 2002 Elsevier Science B.V. All rights reserved.