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We report a molecular switching ensemble whose states may be regulated in synergistic fashion by both protonation and photoirradiation. This allows hierarchical control in both a kinetic and thermodynamic sense. These pseudorotaxane-based molecular devices exploit the so-called Texas-sized molecular box (cyclo[2]-(2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene); 1⁴⁺, studied as its tetrakis-PF₆⁻salt) as the wheel component. Anions of azobenzene-4,4′-dicarboxylic acid (2H⁺•2) or 4,4′-stilbenedicarboxylic acid (2H⁺•3) serve as the threading rod elements. The various forms of 2 and 3 (neutral, monoprotonated, and diprotonated) interact differently with 1⁴⁺, as do the photoinducedcisortransforms of these classic photoactive guests. The net result is a multimodal molecular switch that can bemore »regulated in synergistic fashion through protonation/deprotonation and photoirradiation. The degree of guest protonation is the dominating control factor, with light acting as a secondary regulatory stimulus. The present dual input strategy provides a complement to more traditional orthogonal stimulus-based approaches to molecular switching and allows for the creation of nonbinary stimulus-responsive functional materials.

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Nanocrystalline metals have shown enhanced radiation tolerance as grain boundaries serve as effective defect sinks for removing radiation-induced defects. However, the thermal and radiation stability of nanograins are of concerns since radiation may induce grain boundary migration and grain coarsening in nanocrystalline metals when the grain size falls in the range of several to tens of nanometers. In addition, prior in situ radiation studies on nanocrystalline metals have focused primarily on single heavy ion beam radiations, with little consideration of the helium effect on damage evolution. In this work, we utilized in situ single-beam (1 MeV Kr++) and dual-beam (1more »MeV Kr++ and 12 keV He+) irradiations to investigate the influence of helium on the radiation response and grain coarsening in nanocrystalline Cu at 300 °C. The grain size, orientation, and individual grain boundary character were quantitatively examined before and after irradiations. Statistic results suggest that helium bubbles at grain boundaries and grain interiors may retard the grain coarsening. These findings provide new perspective on the radiation response of nanocrystalline metals.« less

Nanocrystalline and nanolaminated materials show enhanced radiation tolerance compared with their coarse-grained counterparts, since grain boundaries and layer interfaces act as effective defect sinks. Although the effects of layer interface and layer thickness on radiation tolerance of crystalline nanolaminates have been systematically studied, radiation response of crystalline/amorphous nanolaminates is rarely investigated. In this study, we show that irradiation can lead to formation of nanocrystals and nanotwins in amorphous CuNb layers in Cu/amorphous-CuNb nanolaminates. Substantial element segregation is observed in amorphous CuNb layers after irradiation. In Cu layers, both stationary and migrating grain boundaries effectively interact with defects. Furthermore, there ismore »a clear size effect on irradiation-induced crystallization and grain coarsening. In situ studies also show that crystalline/amorphous interfaces can effectively absorb defects without drastic microstructural change, and defect absorption by grain boundary and crystalline/amorphous interface is compared and discussed. Our results show that tailoring layer thickness can enhance radiation tolerance of crystalline/amorphous nanolaminates and can provide insights for constructing crystalline/amorphous nanolaminates under radiation environment.« less