Simplifying and expanding the scope of boron imidazolate framework (BIF) synthesis using mechanochemistry

Abstract

Mechanochemistry enables rapid access to boron imidazolate frameworks (BIFs), including the archetypal materials based on Li and Cu(I) nodes, as well as new, previously unexplored systems based on Ag(I) nodes....

Tribochemical nanolithography: selective mechanochemical removal of photocleavable nitrophenyl protecting groups with 23 nm resolution at speeds of up to 1 mm s−1

“…In recent years there has been an explosion of interest in mechanochemistry, [17][18][19] the mechanical activation of chemical reactivity. [19][20][21][22][23][24][25][26][27][28][29][30][31] In bulk phases, mechanical grinding enables solventless mechanochemical synthesis, 21,32 attracting growing interest as a means to mitigate the environmental impact of chemical processes. 33 At interfaces, tribochemical processes are known to play a role in determining the performance of lubrication systems.…”

Crystallographic and Compositional Dependence of Thermodynamic Stability of [Co(II), Cu(II), and Zn(II)] in 2-Methylimidazole-Containing Zeolitic Imidazolate Frameworks

“…18,27,28 For example, real-time studies of the mechanochemical ball-milling preparation of ZIF-8, a popular ZIF material based on divalent zinc nodes and 2methylimidazolate linkers (MeIm − ), have revealed the sequential formation of the highly porous SOD-topology material ZIF-8, followed by the appearance of katsenite (kat) and finally diamondoid (dia)-topology polymorphs. 17,28,29 A considerable amount of effort has gone into investigating the synthesis of MOFs, 18,29,30 as well as the thermal stability 31 and resistance to structural degradation in water 5 of such materials, often with an emphasis on their kinetic stability. 32 Despite the focus on the kinetics of reactivity, 32 thermodynamic investigations are required to assess whether reactions can take place at all.…”

“…By employing different metal–ligand combinations, , a wide range of frameworks have been prepared with tunable material properties, − from sorption selectivity to material porosity. ,, Moreover, ZIFs and related composites also offer exceptional thermal and hydrothermal stability, including under acidic or basic conditions, , which is considered a prerequisite for any widespread application. , Furthermore, various ZIF polymorphs are accessible through variations of the synthesis conditions. ,, For example, real-time studies of the mechanochemical ball-milling preparation of ZIF-8, a popular ZIF material based on divalent zinc nodes and 2-methylimidazolate linkers (MeIm – ), have revealed the sequential formation of the highly porous SOD-topology material ZIF-8, followed by the appearance of katsenite (kat) and finally diamondoid ( dia )-topology polymorphs. ,, …”

“…A considerable amount of effort has gone into investigating the synthesis of MOFs, ,, as well as the thermal stability and resistance to structural degradation in water of such materials, often with an emphasis on their kinetic stability . Despite the focus on the kinetics of reactivity, thermodynamic investigations are required to assess whether reactions can take place at all.…”

Experimental Investigation of Thermodynamic Stabilization in Boron Imidazolate Frameworks (BIFs) Synthesized by Mechanochemistry

“…21 Fundamentally, the reaction conditions in the solvothermal and mechanochemical approaches are different, which has in some cases enabled the observation of materials and topologies so far only accessible by mechanochemistry. 3,4,22 The sodalite (SOD) and diamondoid (dia) topologies are often observed across both ZIFs and BIFs. 4,22 Structures in the SOD topology are typically much more porous compared to denser frameworks in the dia topology.…”