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

摘要

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 (H2TPyP) 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.How Porefessional: Solutions of copper(II) acetate (CuAcO), 5,10,15,20‐tetra‐4‐pyridyl‐21 H,23H‐porphine (H2TPyP), and fullerenes C70 or C60 produce crystalline precipitates with the compositions CuAcO‐CuTPyP⊃m‐dichlorobenzene (m‐DCB) (1) and CuAcO‐CuTPyP⋅C70⊃m‐DCB⋅CHCl3 (2). The structures of these materials have been determined by X‐ray diffraction to identify the supramolecular interactions that lead to two‐ and three‐dimensional crystal packing motifs. Complexation in the presence of both C60 and C70 leads to preferential intercalation of C70 between the porphyrins.