We have applied in situ monitoring of mechanochemical reactions by high-energy synchrotron powder X-ray diffraction to study the role liquid additives on synthesis archetypal metal-organic framework (MOF) HKUST-1, which was one first and is still among most widely investigated MOF materials be synthesized solvent-free procedures. It shown here how kinetics mechanisms HKUST-1 can influenced milling conditions additives, yielding occasion two new previously undetected intermediate phases...

The milling ball is the catalyst. We introduce a palladium-catalyzed reaction inside mill, which makes catalyst powders, ligands, and solvents obsolete. present facile highly sustainable synthesis concept for C-C coupling reactions, exemplarily showcased Suzuki polymerization of 4-bromo or 4-iodophenylboronic acid giving poly(para-phenylene). Surprisingly, we observe one highest degrees (199) reported so far.

Abstract We report herein quantitative in situ monitoring by simultaneous PXRD and Raman spectroscopy of the mechanochemical reaction between benzoic acid nicotinamide, affording a rich polymorphic system with four new cocrystal polymorphs, multiple phase transformations, variety pathways. After observing polymorphs monitoring, we were able to isolate characterize three most which are not accessible from solution. Relative stabilities among isolated at ambient conditions established slurry...

The past two decades have witnessed a rapid emergence of interest in mechanochemistry-chemical and materials reactivity achieved or sustained by the action mechanical force-which has led to application mechanochemistry almost all areas modern chemical synthesis: from organic, inorganic, organometallic chemistry enzymatic reactions, formation metal-organic frameworks, hybrid perovskites, nanoparticle-based materials. recent success ball milling also raised questions about underlying...

We demonstrate a controllable mechanochemical synthesis of cocrystal polymorphs ascorbic acid (vitamin C) and nicotinamide B3) on different scales without using bulk solvents. Next to the previously described polymorph 1:1 cocrystal, which is one first cocrystals approved for human consumption, we report here new, thermodynamically more stable detected during in situ synchrotron powder X-ray diffraction monitoring milling reactions. The new currently available exclusively by synthesis, its...

The mechanochemical preparation of silver sulfadiazine and dantrolene, two marketed active pharmaceutical ingredients, was investigated by in situ Raman spectroscopy. For the first time, transformations involving highly fluorescent compounds could be studied with a high-resolution system combined unique suitable probe. Moreover, kinetic features process were examined mathematical model allowing to describe chemical changes under mechanical stress. This approach is promising both broaden...

<italic>In situ</italic> Raman monitoring revealed the first cocrystal as an intermediate in a mechanochemical organic reaction.

Using tandem in situ monitoring and isotope-labeled solids, we reveal that mechanochemical ball-milling overcomes inherently slow solid-state diffusion through continuous comminution growth of milled particles. This process occurs with or without a net chemical reaction also between solids liquid additives can be practically used for highly efficient deuterium labeling solids. The presented findings fundamental aspect milling reactions delineate methodology should considered the study mechanisms.

Abstract Recent progress in the field of mechanochemistry has expanded discovery mechanically induced chemical transformations to several areas science. However, a general fundamental understanding how mechanochemical reactions by ball milling occur remained unreached. For this, we have now implemented situ monitoring mechanochemically molecular rearrangement synchrotron X‐ray powder diffraction, Raman spectroscopy, and real‐time temperature sensing. The results this study demonstrate that...

In recent years, mechanochemistry has enriched the toolbox of synthetic chemists, enabling faster and more sustainable access to new materials existing products, including active pharmaceutical ingredients (APIs). However, molecular-level understanding most mechanochemical reactions remains limited, delaying implementation in industrial applications. Herein, we have applied situ monitoring by Raman spectroscopy mechanosynthesis phenytoin, a World Health Organization (WHO) Essential Medicine,...

Copper-catalyzed mechanochemical click reactions using Cu(II), Cu(I) and Cu(0) catalysts have been successfully implemented to provide novel 6-phenyl-2-(trifluoromethyl)quinolines with a phenyl-1,2,3-triazole moiety at O-4 of the quinoline core. Milling procedures proved be significantly more efficient than corresponding solution reactions, up 15-fold gain in yield. Efficiency both milling depended on p-substituent azide reactant, resulting H < Cl Br I reactivity bias. Solid-state catalysis...

Mechanism of C-H bond activation by various PdII catalysts under milling conditions has been studied in situ Raman spectroscopy. Common precursors, that is PdCl2 , [Pd(OAc)2 ]3 (MeCN)2 and [Pd(MeCN)4 ][BF4 ]2 have employed for the one or two bonds an unsymmetrical azobenzene substrate. The was achieved all used precursors their reactivity increases order <PdCl2 <[Pd(MeCN)4 . In monitoring combination with stepwise ex NMR, IR PXRD experiments provided direct probing reaction mechanism...

Inelastic collisions of the milling media in ball provide energy to reaction mixture required for chemical transformations. However, movement also results physical mixing reactants, which may enable a too. Separating two contributions is challenging and gaining direct insight into purely mechanochemically driven reactivity accordingly hindered. Here, we have applied situ monitoring by Raman spectroscopy suitable, mechanically activated, combined kinetic analysis with numerical simulations...

While desolvation process does not influence the magnetism of Ni-MOF-74, amorphization causes partial nickel(<sc>ii</sc>) spin-crossover from<italic>S</italic>= 1 to<italic>S</italic>= 0 and decrease bulk magnetization.

The nucleobase adenine plays a pivotal role in the chemistry of life but is also becoming increasingly interesting as building block synthesis functional solid materials. Although commercially available solid, adenine's solid-state has so far been neglected. In this comprehensive study it shown that most often marketed mixture two polymorphs, one previously known and new polymorph. Both polymorphs exhibit layered structures with different hydrogen-bonding patterns within layers. crystal...

Abstract Das Mahlmaterial ist der Katalysator. In diesem Beitrag stellen wir eine palladiumkatalysierte Reaktion in Kugelmühle vor, bei weder Katalysatorpulver, Liganden, noch Lösungsmittel verwendet werden. Dieses einfache und nachhaltige Konzept zeigen am Beispiel Suzuki‐Polymerisation von 4‐Brom‐ bzw. 4‐Iodphenylboronsäure zu Poly( para ‐phenylen). Überdies beobachten einen höchsten bisher publizierten Polymerisationsgrade (199).

α-Aminophosphonates are an important class of biologically active compounds, attracting considerable attention in medicinal chemistry, by inhibiting enzymes involved amino acid metabolism. Herein, the Kabachnik–Fields domino reaction was investigated mechanochemistry for first-time preparation α-aminophosphonate derivatives high yields and with full selectivity, outperforming comparable solution procedures. The occurs without addition any external catalyst, possibly via a metal-mediated...

Selectivity in mechanochemical cocrystal formation between nicotinamide and anthranilic acid or salicylic was studied using tandem situ reaction monitoring by powder X-ray diffraction (PXRD) Raman spectroscopy. probed offering a competing coformer to previously prepared under competitive conditions where all coformers, different stoichiometric ratios, were introduced together the starting mixture. Reaction paths dependent on mixture composition, we find that of intermediates final product...

For the first time, in situ monitoring of uninterrupted mechanochemical synthesis two bimetallic amidoboranes, M2 Mg(NH2 BH3 )4 (M=Li, Na), by means Raman spectroscopy, has been applied. This approach allowed real-time observation key intermediate phases, and a straightforward follow-up reaction course. Detailed analysis time-dependent spectra revealed two-step mechanism through MNH2 ⋅NH3 adducts as phases which further reacted with MgH2 , giving final products. The intermediates partially...

Solid-state may serve as the reaction medium for selective recognition between model nucleobases.

Performing reactions in the solid state offers largely unexplored possibility of influencing reactivity by manipulating form starting reactants. In this work, we explore use various forms barbituric acid and its effect on reaction paths kinetics a Knoevenagel condensation with vanillin. Modifications included desmotrope, cocrystal, salt as reactant. Comparing these from commercial keto tautomer acid, find that could be accelerated or decelerated, together change mechanism. Exploring...

This study investigates the mechanochemical reaction of hydrogen isotope exchange between solid benzoic acid and liquid heavy water. The systematic change milling conditions revealed that rate scales with frequency mass balls. ball size being always same, faster reactions stem from use higher frequencies heavier kinetic curves are described by a model accounts for statistical, deformational chemical factors involved in transformations. results indicate is driven generation new interface area...

Abstract Recent progress in the field of mechanochemistry has expanded discovery mechanically induced chemical transformations to several areas science. However, a general fundamental understanding how mechanochemical reactions by ball milling occur remained unreached. For this, we have now implemented situ monitoring mechanochemically molecular rearrangement synchrotron X‐ray powder diffraction, Raman spectroscopy, and real‐time temperature sensing. The results this study demonstrate that...

N-H bond activation of gaseous ammonia is achieved at room temperature in a reversible solvent-free reaction using solid dicyclopalladated azobenzene complex. Monitoring the gas-solid real-time by situ solid-state Raman spectroscopy enabled detailed insight into stepwise pathway proceeding to final amido complex via stable diammine intermediate. Gas-solid synthesis allowed for isolation and subsequent structural characterization intermediate product, which presents first dipalladated with...