Converting Second-Order Saddle Points to Transition States: New Principles for the Design of 4π Photoswitches.

Molecular photoswitches have demonstrated potential for storing solar energy at the molecular level, with power densities comparable to commercial batteries and hydroelectric energy storage. However, development of efficient photoswitches is hindered by limitations in cyclability and optical properties of existing materials. We here demonstrate that certain limitations in photoswitches based on electrocyclizations stem from the issue of controlling competition between Woodward-Hoffmann allowed and forbidden pathways.

Predicting Kinetics and Dynamics of Spin-Dependent Processes.

ConspectusPredicting mechanisms and rates of nonadiabatic spin-dependent processes including photoinduced intersystem crossings, thermally activated spin-forbidden reactions, and spin crossovers in metal centers is a very active field of research. These processes play critical roles in transition-metal-based and metalloenzymatic catalysis, molecular magnets, light-harvesting materials, organic light-emitting diodes, photosensitizers for photodynamic therapy, and many other applications. Therefore, accurate modeling of spin-dependent processes in complex systems and on different time scales is important for many problems in chemistry, biochemistry, and materials sciences.

The role of the intermediate triplet state in iron-catalyzed multi-state C-H activation.

Efficient activation and functionalization of the C-H bond under mild conditions are of a great interest in chemical synthesis. We investigate the previously proposed spin-accelerated activation of the C(sp)-H bond by a Fe(II)-based catalyst to clarify the role of the intermediate triplet state in the reaction mechanism. High-level electronic structure calculations on a small model of a catalytic system utilizing the coupled cluster with the single, double, and perturbative triple excitations [CCSD(T)] are used to select the density functional for the full-size model.

Bacteriostatic Effects of Apatite-Covered Ag/AgBr/TiO Nanocomposite in the Dark: Anomaly in Bacterial Motility.

In this paper, we report a unique property of inactivating Gram-positive/negative bacteria in the dark via apatite-covered Ag/AgBr/TiO nanocomposites (AAAT). We demonstrate that the inactivation mechanism is bacteriostatic based on the cellular integrity and motility of bacteria, low toxicity and high durability of AAAT. From straight observations, the catalytic loading affects the bacterial replication and cell envelope as well as inducing an anomaly in bacterial motility (continuous rotation) for both types of bacteria.