Use of the tetrahedral ligand tetrakis(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 Mn6(ttpm)3⋅5 DMF⋅3 H2O (1) and Cu[(Cu4Cl)(ttpm)2]2⋅CuCl2⋅5 DMF⋅11 H2O (2) (H4ttpm=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 Cu4(ttpm)2⋅0.7 CuCl2 (2 d), a microporous material exhibiting a high surface area and significant hydrogen uptake.
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