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Nonsymmetrical oxygen-bridged binuclear copper centers have been proposed and modeled as intermediates and transition states in several C─H oxidation pathways, leading to the postulation that structural dissymmetry enhances the reactivity of the bridging oxygen. However, experimentally characterizing the structure and reactivity of these transient species is remarkably challenging. Here, we report the high-pressure synthesis of a metastable nonsymmetrical dicopper-μ-oxo compound with exceptional reactivity toward the mono-oxygenation of aliphatic C─H bonds. The nonequivalent coordination environment of copper stabilizes localized mixed valency and greatly enhances the hydrogen atom abstraction activity of the bridging oxygen, enabling room-temperature hydroxylation of methane under pressure. These findings highlight the role of dissymmetry in the reactivity of binuclear copper centers and demonstrate precise control of molecular structures by mechanical means. 

BackgroundThe fast-changing labor market highlights the need for an in-depth understanding of occupational mobility impacted by technological change. However, we lack a multidimensional classification scheme that considers similarities of occupations comprehensively, which prevents us from predicting employment trends and mobility across occupations. This study fills the gap by examining employment trends based on similarities between occupations. MethodWe first demonstrated a new method that clusters 756 occupation titles based on knowledge, skills, abilities, education, experience, training, activities, values, and interests. We used the Principal Component Analysis to categorize occupations in the Standard Occupational Classification, which is grouped into a four-level hierarchy. Then, we paired the occupation clusters with the occupational employment projections provided by the U.S. Bureau of Labor Statistics. We analyzed how employment would change and what factors affect the employment changes within occupation groups. Particularly, we specified factors related to technological changes. ResultsThe results reveal that technological change accounts for significant job losses in some clusters. This poses occupational mobility challenges for workers in these jobs at present. Job losses for nearly 60% of current employment will occur in low-skill, low-wage occupational groups. Meanwhile, many mid-skilled and highly skilled jobs are projected to grow in the next ten years. ConclusionOur results demonstrate the utility of our occupational classification scheme. Furthermore, it suggests a critical need for skills upgrading and workforce development for workers in declining jobs. Special attention should be paid to vulnerable workers, such as older individuals and minorities. 

Barocaloric effects─solid-state thermal changes induced by the application and removal of hydrostatic pressure─offer the potential for energy-efficient heating and cooling without relying on volatile refrigerants. Here, we report that dialkylammonium halides─organic salts featuring bilayers of alkyl chains templated through hydrogen bonds to halide anions─display large, reversible, and tunable barocaloric effects near ambient temperature. The conformational flexibility and soft nature of the weakly confined hydrocarbons give rise to order–disorder phase transitions in the solid state that are associated with substantial entropy changes (>200 J kg–1 K–1) and high sensitivity to pressure (>24 K kbar–1), the combination of which drives strong barocaloric effects at relatively low pressures. Through high-pressure calorimetry, X-ray diffraction, and Raman spectroscopy, we investigate the structural factors that influence pressure-induced phase transitions of select dialkylammonium halides and evaluate the magnitude and reversibility of their barocaloric effects. Furthermore, we characterize the cyclability of thin-film samples under aggressive conditions (heating rate of 3500 K s–1 and over 11,000 cycles) using nanocalorimetry. Taken together, these results establish dialkylammonium halides as a promising class of pressure-responsive thermal materials. 

Abstract Twisted moiré photonic crystal is an optical analog of twisted graphene or twisted transition metal dichalcogenide bilayers. In this paper, we report the fabrication of twisted moiré photonic crystals and randomized moiré photonic crystals and their use in enhanced extraction of light in light-emitting diodes (LEDs). Fractional diffraction orders from randomized moiré photonic crystals are more uniform than those from moiré photonic crystals. Extraction efficiencies of 76.5%, 77.8% and 79.5% into glass substrate are predicted in simulations of LED patterned with twisted moiré photonic crystals, defect-containing photonic crystals and random moiré photonic crystals, respectively, at 584 nm. Extraction efficiencies of optically pumped LEDs with 2D perovskite (BA)₂(MA)_n−1Pb_nI_3n+1ofn= 3 and (5-(2′-pyridyl)-tetrazolato)(3-CF₃−5-(2′-pyridyl)pyrazolato) platinum(II) (PtD) have been measured.