SUPRAMOLECULAR NETWORKS OF OCTAHYDROXY PORPHYRINS

Multifunctionalized octahydroxy porphyrins, 10,15,20-tetrakis(2',6'-di hydroxypheny)-porphyrin, H2T(2',6'-DHP)P, and 0,15,20-tetrakis-(3',5'- dihydroxyphenyl)porphyrin, H2T(3',5'-DHP)P, have been developed as sol id state building blocks for the self-assembly of hydrogen bonded supr amolecular networks. A series of solid state X-ray structures of these porphyrins with various solvates show strong inter-porphyrin interact ions through their peripheral hydroxyl substituents by means of direct ional hydrogen bonding. The position of the hydroxyl groups and the na ture of the lattice guest (i.e, solvate) have dramatic influences on t he molecular packing and the porosity of the structures. In particular , with ethyl acetate as solvate, the crystal structure of H2T(3',5'-DH P)P exhibits a one dimensional columnar network, whereas H2T(2',6'-DHP )P shows essentially a two dimensional, hydrogen-bonded, layered struc ture. With benzonitrile as solvate, the structure of H2T(3',5'-DHP)P c hanges substantially to a two dimensional corrugated structure in orde r to accommodate a larger pore size. The pore volumes filled by solvat e in these structures are exceptionally large: 56%, 61%, and 67% of th e unit cell volume, respectively. Crystal structure data for H2T(3',5' -DHP)P . 5 EtOAc: C64H70N4O18, M = 1183.24, triclinic, P (1) over bar, a = 7.245 (2) Angstrom, b = 14.727 (3) Angstrom, c = 14.835 (4) Angst rom, alpha = 90.18 (2)degrees, beta = 92.90 (2)degrees and gamma = 90. 02 (2)degrees, V = 1580.8(7) A(3), Z = 1; R1 = 0.113, wR2 = 0.280 (on 2588, I > 2 sigma(I) observed data). For H2T(2',6'-DHP)P . 4 EtOAc: C6 0H62N4O16, M = 1095.14, triclinic, P (1) over bar, a = 13.736 (3) Angs trom, b = 14.032 (3) Angstrom, c = 17.029 (3) Angstrom, alpha = 93.77 (3)degrees, beta = 110.92 (3)degrees and gamma = 111.81 (3)degrees, V = 2770.9 (10) A(3), Z = 2; R1 = 0.045, wR2 = 0.112 (on 6260, I > 2 sig ma(I) observed data). For H2T(3',5'-DHP)P . 7 C7H5N: C93H65N11O8, M = 1464.56, monoclinic, P2(1)/m, a = 11.105 (4) Angstrom, b = 25.744 (7) Angstrom, c = 14.022 (3) Angstrom, beta = 108.09 (2)degrees, V = 3811( 2) A(3), Z = 2; R1 = 0.062, wR2 = 0.130 (on 2588, I > 2 sigma(I) obser ved data).