Mechanosynthesis and photophysics of colour-tunable photoluminescent group 13 metal complexes with sterically demanding salen and salophen ligands.

A series of four photoluminescent Al and In complexes were synthesised using an environmentally-benign mechanosynthesis strategy. Sterically crowded 3,5-di-tert-butyl functionalised salophen and salen ligands and their respective complexes have been synthesised in the solid-state and fully characterised. Subsequent photophysics and electrochemistry studies of the resulting complexes suggest that these new group 13 complexes can be viable alternatives to traditional photoluminescent complexes based on expensive and low abundant noble metals. The herein-reported strategy avoids the use of organic solvents and provides a process with low environmental impact and enhanced energy efficiency.

Temperature-Controlled Mechanochemistry Unlocks the Nickel-Catalyzed Suzuki-Miyaura-Type Coupling of Aryl Sulfamates at Different Scales.

Several mechanochemically heated processes have been published in recent years. However, precise control over the mechanochemical catalysed coupling reactions remained elusive. A recent report from Leitch, Browne and co-workers demonstrated how a programmable jar heater manifold delivers an efficient methodology for the Suzuki-Miyaura-type cross coupling reaction of aryl sulfamates and aryl boronic acid species. This methodology can be readily upscaled 200-fold using twin-screw extrusion methodologies.

Tinkering with Mechanochemical Tools for Scale Up.

Mechanochemistry provides an environmentally benign platform to develop more sustainable chemical processes by limiting raw materials, energy use, and waste generation while using physically smaller equipment. A continuously growing research community has steadily showcased examples of beneficial mechanochemistry applications at both the laboratory and the preparative scale. In contrast to solution-based chemistry, mechanochemical processes have not yet been standardized, and thus scaling up is still a nascent discipline. The purpose of this Minireview is to highlight similarities, differences and challenges of the various approaches that have been successfully applied for a range of chemical applications at various scales. We hope to provide a discussion starting point for those interested in further developing mechanochemical processes for commercial use and/or industrialisation.

Carbon dioxide sequestration by mineral carbonation via iron complexation using bipyridine chelating ligands.

An innovative mineral carbonation method was developed to synthesize iron(II) carbonate (FeCO3) by cation complexation using 2,2'-bipyridine as ligand. First, complexes of iron(II) and different ligands were theoretically analyzed and discounted in terms of their temperature and pH-dependent stabilities, iron-ligand interactions, possible by-products and difficulty of analysis, choosing 2,2'-bipyridine as the most suitable ligand. Then, the Job plot was used to verify the complex formula. The stability of [Fe(bipy)3]2+ at pH 1-12 was further monitored for 7 days using UV-Vis and IR spectroscopy. Good stability was observed between pH 3 and 8, decreasing within pH 9-12 where the carbonation reaction occurs. Finally, the reaction between Na2CO3 and [Fe(bipy)3]2+ was performed at 21, 60, and 80 °C and pH 9-12. The total inorganic carbon measured after 2 h shows that the best carbonate conversion (50%) occurred at 80 °C and pH 11, being the most suitable conditions for carbon sequestration. SEM-EDS and XRD were used to examine the effect of synthesis parameters on the morphology and composition of FeCO3. The FeCO3 particle size increased from 10 µm at 21 °C to 26 and 170 µm at 60 and 80 °C respectively with no pH dependence. In addition, EDS analysis supported the carbonate identity, whose amorphous nature was confirmed by XRD. These results would help prevent the iron hydroxide precipitation problem during mineral carbonation using iron-rich silicates. These results are promising for its application as a carbon sequestration method with a CO2 uptake of around 50% obtaining Fe-rich carbonate.

Correction: Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn).

[This corrects the article DOI: 10.1039/D3SC02709K.].

Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn).

Iconic Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge (1), Sn (2), Pb (3)) have been efficiently prepared from GeCl2·(1,4-dioxane), SnCl2 or PbCl2 and Li{N(SiMe3)2} via a completely solvent-free one-pot mechanochemical route followed by sublimation. This fast, high-yielding and scalable approach (2 has been prepared in a 100 mmol scale), which involves a small environmental footprint, represents a remarkable improvement over any synthetic route reported over the last five decades, being a so far rare example of the use of mechanochemistry in the realm of main group chemistry. This solventless route has been successfully extended to the preparation of other heavier tetrylenes, such as ECl{N(SiMe3)2} (E = Ge (4), Sn (5)).