Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids: MIL-53 or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}x·H2Oy

Abstract

The first three-dimensional chromium(III) dicarboxylate, MIL-53as or Cr^III(OH)·{O₂C−C₆H₄−CO₂}·{HO₂C−C₆H₄−CO₂H}_0.75, has been obtained under hydrothermal conditions (as: as-synthesized). The free acid can be removed by calcination giving the resulting solid, MIL-53ht or Cr^III(OH)·{O₂C−C₆H₄−CO₂}. At room temperature, MIL-53ht adsorbs atmospheric water immediately to give Cr^III(OH)·{O₂C−C₆H₄−CO₂}·H₂O or MIL-53lt (lt: low-temperature form, ht: high-temperature form). Both structures, which have been determined by using X-ray powder diffraction data, are built up from chains of chromium(III) octahedra linked through terephthalate dianions. This creates a three-dimensional structure with an array of one-dimensional large pore channels filled with free disordered terephthalic molecules (MIL-53as) or water molecules (MIL-53lt); when the free molecules are removed, this leads to a nanoporous solid (MIL-53ht) with a Langmuir surface area over 1500 m²/g. The transition between the hydrated form (MIL-53lt) and the anhydrous solid (MIL-53ht) is fully reversible and followed by a very high breathing effect (more than 5 Å), the pores being clipped in the presence of water molecules (MIL-53lt) and reopened when the channels are empty (MIL-53ht). The thermal behavior of the two solids has been investigated using TGA and X-ray thermodiffractometry. The sorption properties of MIL-53lt have also been studied using several organic solvents. Finally, magnetism measurements performed on MIL-53as and MIL-53lt revealed that these two phases are antiferromagnetic with Néel temperatures T_N of 65 and 55 K, respectively. Crystal data for MIL-53as is as follows: orthorhombic space group Pnam with a = 17.340(1) Å, b = 12.178(1) Å, c = 6.822(1) Å, and Z = 4. Crystal data for MIL-53ht is as follows: orthorhombic space group Imcm with a = 16.733(1) Å, b = 13.038(1) Å, c = 6.812(1) Å, and Z = 4. Crystal data for MIL-53lt is as follows: monoclinic space group C2/c with a = 19.685(4) Å, b = 7.849(1) Å, c = 6.782(1) Å, β = 104.90(1)°, and Z = 4.