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Recently, polymer mechanochemistry has attracted much scientific interest due to its potential to develop degradable polymers. When the two ends of a polymer chain experience a linear pulling stress, molecular strain builds up, at sufficiently strong force, a bond scission of the weakest covalent bond results. In contrast, bond‐breaking events triggered by conformational stress are much less explored. Here, we discovered that a Zn salen complex would undergo conformational switching upon allosteric complexation with alkanediammonium guests. By controlling the guest chain length, the torsional strain experienced by Zn complex can be modulated to induce bond cleavage with chemical stimulus, and reactivity trend is predicted by conformational analysis derived by DFT calculation. Such strain‐release reactivity by a Zn(salen) complex initiated by guest binding is reminiscent of conformation‐induced reactivity of enzymes to enable chemical events that are otherwise inhibited. [ABSTRACT FROM AUTHOR]

Recently, polymer mechanochemistry has attracted much scientific interest due to its potential to develop degradable polymers. When the two ends of a polymer chain experience a linear pulling stress, molecular strain builds up, at sufficiently strong force, a bond scission of the weakest covalent bond results. In contrast, bond‐breaking events triggered by conformational stress are much less explored. Here, we discovered that a Zn salen complex would undergo conformational switching upon allosteric complexation with alkanediammonium guests. By controlling the guest chain length, the torsional strain experienced by Zn complex can be modulated to induce bond cleavage with chemical stimulus, and reactivity trend is predicted by conformational analysis derived by DFT calculation. Such strain‐release reactivity by a Zn(salen) complex initiated by guest binding is reminiscent of conformation‐induced reactivity of enzymes to enable chemical events that are otherwise inhibited. [ABSTRACT FROM AUTHOR]

Chiral vicinal diamines, a unique class of optically-active building blocks, play a crucial role in material design, pharmaceutical, and catalysis. Traditionally, their syntheses are all solvent-based approaches, which make organic solvent an indispensable part of their production. As part of our program aiming to develop chemical processes with reduced carbon footprints, we recently reported a highly practical and environmentally-friendly synthetic route to chiral vicinal diamines by solvent-free mechanochemical diaza-Cope rearrangement. We herein showed that a new protocol by co-milling with common laboratory solid additives, such as silica gel, can significantly enhance the efficiency of the reaction, compared to reactions in the absence of additives. One possible explanation is the Lewis acidic nature of additives that accelerates a key Schiff base formation step. Reaction monitoring experiments tracing all the reaction species, including reactants, intermediates, and product, suggested that the reaction profile is distinctly different from ball-milling reactions without additives. Collectively, this work demonstrated that additive effect is a powerful tool to manipulate a reaction pathway in mechanochemical diazo-Cope rearrangement pathway, and this is expected to find broad interest in organic synthesis using mechanical force as an energy input. [ABSTRACT FROM AUTHOR]

Metal-sulfides electrode materials usually suffer from poor cyclability and low rate capability in rechargeable batteries as a result of the pulverization of active materials and the loss of sulfur material induced by polysulfide dissolution. Herein, we reported a delicate and scalable route for rational design of CuS/graphene composites. Hierarchical CuS microparticles comprising of large amounts of self-assembled and well-arranged nanosheets uniformly mixed with flexible graphene layers. The obtained CuS/graphene electrodes exhibited high specific capacities, excellent cycling stability and desirable rate capability when being evaluated as anode materials for lithium-ion batteries. The high specific capacities of 568 mA h g −1 after 100 cycles at 50 mA g −1 and 143 mA h g −1 at 1000 mA g −1 (in rate testing) were achieved, suggesting a very promising candidate for high-performance lithium-ion batteries. The rationally designed structures of the CuS/graphene composites offered stable-hosts for Li + insertion and alleviated the volume changes upon cycling. The presence of the graphene in composite not only constructed conductive paths and a network for fast transport of Li + , but also effectively reduced the dissolution of polysulfides into electrolyte. This graphene-based composite with hierarchical structure could be used as a safe, low-cost, and versatile material for extensively potential applications. [ABSTRACT FROM AUTHOR]