Acid-based Metal-organic Frameworks Research Articles

Efficient synthesis of aluminum- and zinc-containing metal-organic frameworks

A convenient method has been proposed for the synthesis of aluminum- and zinc-containing terephthalic acid-based metal-organic frameworks. The method offers high productivity and high product yield. Materials produced by this method have been characterized by physicochemical techniques, and their sorption capacity has been assessed.

The ionothermal synthesis, structure, and magnetism-structure relationship of two biphenyl tetracarboxylic acid-based metal-organic frameworks.

Two new metal-organic frameworks (1-2) were ionothermally obtained by the reaction of a biphenyltetracarboxylic sodium (Na4BPTC) ligand and M(OOCCH3)2 (M = Co(1) and Mn(2)). Crystal structure analysis reveals that 1 is a Co3Na6 unit-based three dimensional heterometallic MOF, while 2 exhibits a {Mn(COO)n} chain-based three-dimensional framework. Furthermore, the magnetic measurement shows that both of them have anti-ferromagnetic properties. A combination of Density Functional Theory (DFT) and Quantum Monte Carlo (QMC) simulation uncovers that in 2 the coupling parameters between two adjacent Mn(II) ions are J1 = -2.0 cm(-1) and J2 = -1.6 cm(-1), and the magnetism mainly originates from the propagation of Mn(II) ions by the super-exchange of carboxylates. Interestingly, the superexchange modes of J1 and J2 are different. Two spin nets of -/+/- dominate in the coupling for J1, while for J2 there are two spin nets of -/+/- and one spin net of +/-/+.

The influence of the enantiomeric ratio of an organic ligand on the structure and chirality of metal-organic frameworks.

We have prepared three distinct polyamino acid-based metal-organic frameworks (MOFs) with different chiralities and porosities using the same chemistry, by simply modifying the enantiomeric ratio of the chiral organic ligand used.

Relating pore hydrophilicity with vapour adsorption capacity in a series of amino acid based metal organic frameworks

A new Zn based porous homochiral metal–organic framework, ThrZnOAc, belonging to unh topology, has been synthesized using pyridyl functionalized threonine and Zn(OAc)2 as the metal precursor. Stepwise substitution of the homochiral MOF backbone by simply changing the sidearm of the amino acids (isopropyl in the case of valine, methyl in alanine and hydroxyethyl in threonine) resulted in increased water adsorption in ThrZnOAc compared to the previously reported ValZnOAc/AlaZnOAc. Extensive solvent sorption isotherms (water, methanol, isopropanol and toluene) have been carried out, which revealed high solvophilic interaction with polar solvents in ThrZnOAc due to the polar pore [2-hydroxyethyl {–CH(OH)CH3} sidearm of the amino acid], which is not prominent in the corresponding valine/alanine counterparts. The aforementioned functionalization in a series of isostructural amino acid based MOFs with the only difference being in the sidearm and their emergence as enhanced solvophilic materials is unprecedented in the MOF literature.