Supramolecular Porphyrin-Based Metal-Organic Frameworks with Fullerenes: Crystal Structures and Preferential Intercalation of C70.

The syntheses and characterization of two new porphyrin-based metal-organic frameworks (P-MOFs), through the complexation of 5,10,15,20-tetra-4-pyridyl-21 H,23 H-porphine (H2 TPyP) and copper(II) acetate (CuAcO) in the presence of the fullerenes C60 or C70 are reported. Complex 1 was synthesized in conjunction with C60 , and this reaction produced a two-dimensional (2D) porous structure with the composition CuAcO-CuTPyP⊃m-dichlorobenzene (m-DCB), in which C60 molecules were not intercalated. Complex 2 was synthesized in the presence of C70 , generating a three-dimensional (3D) porous structure, in which C70 was intercalated, with the composition CuAcO-CuTPyP⋅C70 ⊃m-DCB⋅CHCl3 . The structures of these materials were determined by X-ray diffraction to identify the supramolecular interactions that lead to 2D and 3D crystal packing motifs. When a combination of C60 and C70 was employed, C70 was found to be preferentially intercalated between the porphyrins.