Dynamics and Entropy of Cyclohexane Rings Control pH-Responsive Reactivity.

Activation entropy (ΔS ‡) is not normally considered the main factor in determining the reactivity of unimolecular reactions. Here, we report that the intramolecular degradation of six-membered ring compounds is mainly determined by the ΔS ‡, which is strongly influenced by the ring-flipping motion and substituent geometry. Starting from the unique difference between the pH-dependent degradation kinetics of geometric isomers of 1,2-cyclohexanecarboxylic acid amide (1,2-CHCAA), where only the cis isomer can readily degrade under weakly acidic conditions (pH < 5.5), we found that the difference originated from the large difference in ΔS ‡ of 16.02 cal·mol-1·K-1. While cis-1,2-CHCAA maintains a preference for the classical chair cyclohexane conformation, trans-1,2-CHCAA shows dynamic interconversion between the chair and twisted boat conformations, which was supported by both MD simulations and VT-NMR analysis. Steric repulsion between the bulky 1,2-substituents of the trans isomer is one of the main reasons for the reduced energy barrier between ring conformations that facilitates dynamic ring inversion motions. Consequently, the more dynamic trans isomer exhibits much a larger loss in entropy during the activation process due to the prepositioning of the reactant than the cis isomer, and the pH-dependent degradation of the trans isomer is effectively suppressed. When the ring inversion motion is inhibited by an additional methyl substituent on the cyclohexane ring, the pH degradability can be dramatically enhanced for even the trans isomer. This study shows a unique example in which spatial arrangement and dynamic properties can strongly influence molecular reactivity in unimolecular reactions, and it will be helpful for the future design of a reactive structure depending on dynamic conformational changes.

Transformation of a proton insulator to a conductor via reversible amorphous to crystalline structure transformation of MOFs.

In this study, a successful proton conduction modulation of MOFs, from an ionic insulator to an ionic conductor, is demonstrated through their structural transformation. It is shown that the reversible structural change from amorphous to crystalline phases allows for the reversible proton conduction modulation of MOFs. Moreover, the proton conduction mechanism of the ionic conductor phase is elucidated by 2H NMR analysis.

In Situ Observation of the Effect of Accelerating Voltage on Electron Beam Damage of Layered Cathode Materials for Lithium-Ion Batteries.

Electron beam damage from transmission electron microscopy of layered lithium transition-metal oxides is a threshold phenomenon that depends on the electron beam energy, which we demonstrate in this study by varying the accelerating voltage of a scanning transmission electron microscope. The electron beam irradiation experiment shows that Ni in LiNiO2 has much lower threshold energy for displacement than Co in LiCoO2, which is supported by DFT calculations predicting that Ni has lower migration energy. The transition-metal ions are reduced from the oxidation state of +3 to +2 during migration from their original positions to the lithium sites, and Ni is more easily reduced than Co because of its electronic configuration. In addition, the high-energy electron beam induces oxygen release, which is another symptom of degradation of materials that occurs more strongly in Ni-containing materials with ion displacement.