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

Abstract

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 +/-/+.

Four new metal–organic frameworks based on bi-, tetra-, penta-, and hexa-nuclear clusters derived from 5-(phenyldiazenyl)isophthalic acid: syntheses, structures and properties

“…127 may originate from the multiple superexchange interactions between the Mn(II) cations in the Mn 2 (COO) 4 cluster by the µ 2η 1 :η 1 -COO - 54. …”

Assembling Metal–Organic Frameworks in Ionic Liquids and Supercritical CO2

“…[35,36,38] Compared with the conventional methods of hydrothermal or solvothermals ynthesis, ILs as media for MOF synthesis have many advantages owing to their unique properties such as the ability to simultaneously dissolve both organic and inorganic precursors, high designability,h igh thermal and chemical stability,h igh boilingp oint, and extremely low volatility. [39][40][41][42][43] The resultingM OF structures [44] and properties [45] depend on the ionothermal conditions, especially the features of ILs. [46][47][48][49][50][51] Moreover,M OFs with ILs confined inside nanocages are promising candidates for functionalized MOF materials, [52] whichh ave potential applications in gas adsorption, [53,54] heterogeneous catalysis, [55,56] and electrochemical devices.…”

“…Up to now, a great number of MOFs have been synthesized by means of ionothermal synthesis . Compared with the conventional methods of hydrothermal or solvothermal synthesis, ILs as media for MOF synthesis have many advantages owing to their unique properties such as the ability to simultaneously dissolve both organic and inorganic precursors, high designability, high thermal and chemical stability, high boiling point, and extremely low volatility . The resulting MOF structures and properties depend on the ionothermal conditions, especially the features of ILs .…”

The Preparation of Porous Sol-Gel Silica with Metal Organic Framework MIL-101(Cr) by Microwave-Assisted Hydrothermal Method for Adsorption Chillers

“…MOF materials have been synthesized by various methods, including microwave-assisted hydrothermal [ 15 , 16 ], hydrothermal [ 17 , 18 ], electrochemical [ 19 , 20 ], sonochemical [ 21 ], mechanochemical [ 22 , 23 , 24 ], ionothermal [ 25 , 26 , 27 , 28 ], drygel conversion [ 29 , 30 ], and microfluidic [ 31 ] approaches. Among these fabrication techniques, microwave-assisted hydrothermal methods offer a number of advantages other than synthetic routes, particularly in the case of MOFs [ 10 ].…”