Syntheses and electronic structures of macrocyclic metal complexes with fullerene

New cocrystallines are reported that contain C60 with anti-formed macrocyclic metal complexes of octaethylporphyrin (OEP). From the results of the electronic structure obtained using a DV-Xα molecular orbital calculation, the configuration of the OEP in a cocrystalline of C60 with Ag(II)(OEP) or Ni(II)(OEP) is predicted to be the anti-formed structure. It is shown that the anti-formed configuration of the OEPs can be confirmed in Ag(II)(OEP)·C60·2C6H6 and 2Ni(II)(OEP)·C60·2C6H5Cl according to a structural prediction we have made by means of electronic structure calculations using the DV-Xα method. It is also revealed that the C60 is located at the closest approach to the centered atom involving the 5:6 carbon ring junction in these cocrystallines. Using the DV-Xα method, it is predicted that new types of π–d material can be produced. The material should have high conductivity and a significant magnetic moment via the π–d interaction in the charge transfer salt of [Cr(III)(Por)]+[C60]−.