Mechanosynthesis is a powerful alternative to traditional solvent-based synthesis as it allows for higher yields in shorter reaction times, while minimizing the use of solvents. Although mechanochemical routes are becoming increasingly mainstream in synthetic laboratories, up-scaled examples for main group complexes are still rare. Here, motivated by the practical implementation of mechanosynthesis, we demonstrated the synthesis of salen and salophen complexes. The herein reported synthesis displays low E-factor and process mass intensity compared to conventional solution methods. In addition, analyses evaluating environmental parameters, energy consumption, and production cost have been performed, showing the multiple advantages mechanochemistry has over conventional solution-based synthesis.

We have synthesized ac ompletely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, N i Pr,N t Bu and NPh bridging groups.Inaddition, the first NH-bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species display highly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from % 6t o% 10). Moreover, these species exhibit pronounced topological changes when aw eak non-bonding NH•••p aryl interaction is introduced. Finally,t he NH-bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes. Our results underscore these species as promising hydrogen bond donors for supramolecular host-guest applications.

A series of four photoluminescent Al and In complexes were synthesised using an environmentally-benign mechanosynthetic strategy. Both the sterically crowded 3,5-di-tert-butyl functionalised salophen, salen ligands and the complexes are synthesised...

We have synthesized ac ompletely new family of acyclic trimeric cyclodiphosphazane compounds comprising NH, N i Pr,N t Bu and NPh bridging groups.Inaddition, the first NH-bridged acyclic dimeric cyclophosphazane has been produced. The trimeric species displayh ighly tuneable characteristics so that the distance between the terminal N(H)R moieties can be readily modulated by the steric bulk present in the bridging groups (ranging from % 6to% 10). Moreover,these species exhibit pronounced topological changes when aw eak non-bonding NH•••p aryl interaction is introduced. Finally,the NH-bridged chloride binding affinities have been calculated and benchmarked along with the existing experimental data available for monomeric cyclodiphosphazanes.O ur results underscore these species as promising hydrogen bond donors for supramolecular host-guest applications.

Inorganic macrocycles remain challenging synthetic targets due to the limited number of strategies reported for their syntheses. Among these species, large fully inorganic cyclodiphosphazane macrocycles have been experimentally and theoretically highlighted as promising candidates for supramolecular chemistry. In contrast, their hybrid organic–inorganic counterparts are lagging behind due to the lack of synthetic routes capable of controlling the size and topological arrangement (i.e., folded vs unfolded) of the target macrocycle, rendering the synthesis of differently sized macrocycles a tedious screening process. Herein, we report—as a proof-of-concept—the combination of pre-arranged building blocks and a two-step synthetic route to rationally enable access a large unfolded tetrameric macrocycle, which is not accessible via conventional synthetic strategies. The obtained macrocycle hybrid cyclodiphosphazane macrocycle, cis-[μ-P(μ-NtBu)]2(μ-p-OC6H4C(O)O)]4[μ-P(μ-NtBu)]2 (4), displays an unfolded open-face cavity area of 110.1 Å2. Preliminary theoretical host–guest studies with the dication [MeNC5H4]22+ suggest compound 4 as a viable candidate for the synthesis of hybrid proto-rotaxanes species based on phosphazane building blocks.