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

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Abstract
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.