A novel Zr-chain based MOF, namely MIL-163, was designed and successfully synthesized using a bis-1,2,3-trioxobenzene ligand. Endowed with large square-shaped channels of 12 Å width, it shows remarkable water uptake (ca. 0.6 cm(3) g(-1) at saturating vapor pressure) and a remarkable stability in simulated physiological media, where archetypical Zr carboxylate MOFs readily degrade.

A microporous magnesium gallate MOF was prepared from highly biocompatible reagents under environmentally friendly conditions. Its slow degradation in physiological fluids leads to the release of gallic acid and hence a high antioxidant activity, which was illustrated in the HL-60 cell line.

The reactivity under solvothermal conditions of the ZrIV ion with the naturally occurring gallic acid ligand has been evaluated in depth. The study led to the isolation of four microcrystalline hydroxycarboxylate‐based coordination polymers (MIL‐151 to ‐154). Through the use of a combination of solid‐state NMR and high‐resolution X‐ray powder diffraction analyses, the structures of two of these phases (MIL‐153, MIL‐154) were solved. In both cases, the gallol motifs favour the formation of rod‐like inorganic units built up from ZrO8 polyhedra. Although one compound (MIL‐151) was found to be microporous (SBET ≈ 470 m2 g–1), its poor crystallinity prevented comprehensive structural analysis. Nevertheless, a comparison of its physicochemical features with those of the fully characterized solids allows a plausible structural model to be proposed.