Rational Synthesis of Mixed-Metal Microporous Metal–Organic Frameworks with Controlled Composition Using Mechanochemistry

Abstract

Metal-Organic Frameworks Using Pre-Assembled Precursors. ChemRxiv. Preprint. Ball milling mechanochemistry enables enables targeted, rapid synthesis of mixed-metal metal-organic frameworks (MOFs) with controllable stoichiometric composition. Specifically, the use of ball milling enabled the use of pre-assembled coordination polymers of zinc, magnesium, nickel(II) and cobalt(II) as precursors in an innovative mechanochemical strategy for the deliberate assembly of mixed-metal MOF-74 materials comprised of pairs of transition of main group metals in a pre-determinmed 1:1 stoichiometric ratio, including ZnMg-, ZnCo, ZnCu, MgZn-, MgCo-, MgCa-, NiZn-,NiMg-, NiCo-, CoZn-, CoMg-and CoCu-MOF-74. While this is the first example of target-oriented MOF synthesis using mechanochemistry, it also provides an entry to controlling the stoichiometric composition of mixed-metal frameworks. File list (2) download file view on ChemRxiv manuscript_ChemRxiv.pdf (1.09 MiB) download file view on ChemRxiv SI_ChemRxiv.pdf (2.25 MiB) Mechanochemistry enables targeted synthesis of mixed-metal microporous metal-organic frameworks using pre-assembled precursors

Impact of dehydration and mechanical amorphization on the magnetic properties of Ni(ii)-MOF-74

“…32 When the synthesis was performed in 1:1 nickel:ligand ratio and without heating, we were able to isolate [Ni(dhta)(H 2 O) 4 ]•2H 2 O coordination polymer (Ni-INT), which was recently detected and characterized as an intermediate for the mechanochemical preparation of mixed-metal MOF-74 materials. 39 Both products are highly crystalline, as could be seen in Electronic Supplementary Information (ESI) Fig. S1, and benchstable for months.…”

“…1d). 39 We were, however, more focused here on the response of Ni-MOF-74 to mechanical stress and the correlation between the electronic structure and magnetic properties of Ni-MOF-74 material depending on the level of internal crystal structure ordering. We found that evacuated Ni-MOF-74 collapses rapidly under mechanical stress imposed by ball-milling, producing stable mechanochemically-induced amorphous phase am-Ni-MOF-74.…”

Recent advances in process engineering and upcoming applications of metal–organic frameworks

“…It is also possible to use various types of metal sources, such as pure metals, metal oxides, metal hydroxides, metal carbonates, and even insoluble metals [114] . Furthermore, mechanochemical synthesis can be applied to a stoichiometric ratio of mixed distinct metal components to synthesize mixed-metal MOFs by milling [115] . However, if the byproducts also react under the employed conditions, a solvent may be necessary, as is the case for pore activation by solvent exchange.…”

Organic acids under pressure: elastic properties, negative mechanical phenomena and pressure induced phase transitions in the lactic, maleic, succinic and citric acids

“…The pressure induced phase transitions and structural transformations may be advantageously used, for example, in high-pressure synthesis, mechanochemistry and nanotechnology. 35,[119][120][121][122][123][124][125][126][127][128][129][130][131][132][133] Mechanically responsible organic crystals showing macroscopic motion as a response to pressure or deformation are very interesting due to their potential applications in nanotechnology as organic actuators. 98,[130][131][132][133] The mechanical response of molecular crystals, polymers and organic materials related to living organism physiology is of direct and enormous interest for the human being.…”