Structure and Charge Control in Metal-Organic Frameworks Based on the Tetrahedral Ligand Tetrakis(4-tetrazolylphenyl)methane

Use of the tetrahedral ligand tetra kis(4-tetrazolylphenyl)methane enabled isolation of two three-dimensional metal-organic frameworks featuring 4,6- and 4,8-connected nets related to the structures of garnet and fluorite with the formulae Mn-6-(ttpm)(3)center dot 5DMF center dot 3H(2)O (1) and Cu-[(CU4Cl)(ttpm)(2)](2)center dot CuCl2 center dot 5DMF center dot 11H(2)O (2) (H(4)ttpm=tetrakis(4-tetrazolylphenyl)methane). The fluorite-type solid 2 displays an unprecedented post-synthetic transformation in which the negative charge of the framework is reduced by extraction of copper(II) chloride. Desolvation of this compound generates Cu-4(ttpm)(2)center dot 0.7CuCl(2) (2d), a microporous material exhibiting a high surface area and significant hydrogen uptake.