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
19 Oct 2002-Journal of the American Chemical Society (American Chemical Society)-Vol. 124, Iss: 45, pp 13519-13526
TL;DR: The first three-dimensional chromium(III) dicarboxylate, MIL-53as or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C −C 6H4 −CO2H}0.75, has been obtained under hydrothermal conditions (as: as-synthesized).
Abstract: The first three-dimensional chromium(III) dicarboxylate, MIL-53as or CrIII(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 CrIII(OH)·{O2C−C6H4−CO2}. At room temperature, MIL-53ht adsorbs atmospheric water immediately to give CrIII(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 a...
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TL;DR: In this article, it is shown that there is a strong linear correlation between the parameters for bonds from cations to pairs of anions, and this correlation is used to develop an interpolation scheme that allows the estimation of bond-valence parameters for 969 pairs of atoms.
Abstract: Bond-valence parameters which relate bond valences and bond lengths have been derived for a large number of bonds. It is shown that there is a strong linear correlation between the parameters for bonds from cations to pairs of anions. This correlation is used to develop an interpolation scheme that allows the estimation of bond-valence parameters for 969 pairs of atoms. A complete listing of these parameters is given.
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Abstract: Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.
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TL;DR: In this paper, the authors compared the performance of six profile functions, including the pseudo-Voigt and Pearson VII, in Rietveld refinements with fixed-angle or fixed-wavelength powder diffraction data, obtained with neutrons or with X-rays.
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