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.

New porphyrin-based metal-organic framework with high porosity: 2-D infinite 22.2-A square-grid coordination network.

A new 2-D coordination network with 22.2-A square-grid coordination networks was prepared from a dicopper(II) tetraacetate [Cu2(AcO)4] as a linear linker motif and 5,10,15,20-tetra-4-pyridyl-21H,23H-porphine (H2TPyP) as a four-connected vertex, forming a regular high-porous structure. The characterization by N2 adsorption indicated that this coordination network has uniform micropores and gas adsorption cavities.

Discovery and development of microporous metal carboxylates.

We have found a form of copper(II) terephthalate that occluded an enormous amount of gases such as N2, Ar, O2, and Xe. Copper(II) terephthalate is the first metal complex found capable of adsorbing gases. This complex has opened a new field of adsorbent chemistry and is recognized as a leader in the construction of microporous metal complexes. In extending the route for the synthesis of microporous complexes, we obtained many new porous materials that are widely recognized as useful materials for applications in areas such as gas storage, molecular sieves, catalysis, inclusion complexes, and surface science.