The design of predictable multichromophoric supramolecular arrays of freebase and metallo porphyrins constitutes an essential first step toward the synthesis of light-harvesting complexes. We now report crystal engineering strategies to achieve the synthesis of controllable and predictable porphyrinic multichromophores in the solid state. The coordination complexes of metal halides, MX2 (M = Cd, Hg, Pb; X = Br, I), with freebase tetrapyridylporphyrin (TPyP) form either 1D, [(HgX2)2TPyP]·2TCE, 1, or 2D, [(MX2)TPyP]·4TCE, (M = Pb, 2; Cd, 3) polymeric networks. The porphyrin cavities in these crystalline networks can be selectively populated with various metal cations to generate ordered multiporphyrinic supramolecular arrays without distorting the coordination networks, either by (a) crystallizing the metal halides and TPyP in the presence of suitable metal salts or by (b) reacting metal halides with a mixture of freebase and metallo porphyrins in specific stoichiometric ratios. A design limit has been reached following approach b, synthesis of the complexes using 100% metalated TPyP results in a change in structure due to intermolecular MTPyP coordination. The UV/vis and fluorescence spectra recorded on partially metalated complexes indicate the presence of the expected absorption and emission bands. Additionally, complex 1 reveals an unusual clathration behavior, wherein the stacking features perpendicular to the porphyrin plane adjust to allow inclusion of variable amounts of identical guest solvent molecules without modification of the layered structure.

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Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation.