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 +/-/+.