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.

Triphenylphosphonium (TPP+) species comprising multiple charges, i.e., bis-TPP+, are predicted to be superior mitochondrial-targeting vectors and are expected to have mitochondrial accumulations 1000-fold greater than TPP+, the current “gold standard”. However, bis-TPP+ vectors linked by short hydrocarbon chains (n < 5) are unable to be taken up by the mitochondria, thus hindering their development as mitochondrial delivery vectors. Through the incorporation of methylated TPP+ moieties (T*PP+), we successfully enabled the accumulation of bis-TPP+ with a short linker chain in isolated mitochondria, as measured by high performance liquid chromatography. These experimental results are further supported by molecular dynamics and ab initio calculations, revealing the strong correlations between mitochondria uptake and molecular volume, surface area, and chemical hardness. Most notably, the molecular volume has been shown to be a strong predictor of accumulation for both mono- and bis-TPP+ salts. Our study underscores the potential of T*PP+ moieties as alternative mitochondrial vectors to overcome low permeation into the mitochondria.

Synchrotron Radiation X-ray Fluorescence (SXRF) imaging is a powerful technique for the visualization of metal complexes in biological systems. However, due to the lack of an endogenous elemental signature for...

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.

Inorganic macrocycles remain largely underdeveloped compared with their organic counterparts due to the challenges involved in their synthesis. Among them, cyclodiphosphazane macrocycles have shown to be promising candidates for supramolecular chemistry applications due to their ability to encapsulate small molecules or ions within their cavities. However, further developments have been handicapped by the lack of synthetic routes to high-order cyclodiphosphazane macrocycles. Moreover, current approaches allow little control over the size of the macrocycles formed. Here we report the synthesis of high-order oxygen-bridged phosphazane macrocycles via a “3 + n cyclisation” (n = 1 and 3). Using this method, an all-PIII high-order hexameric cyclodiphosphazane macrocycle was isolated, displaying a larger macrocyclic cavity than comparable organic crown-ethers. Our approach demonstrates that increasing building block complexity enables precise control over macrocycle size, which will not only generate future developments in both the phosphazane and main group chemistry but also in the fields of supramolecular chemistry.

Triphenylphosphonium (TPP+) moieties are commonly conjugated to drug molecules to confer mitochondrial selectivity due to their positive charge and high lipophilicity. Although optimisation of lipophilicity can be achieved by modifying...

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.