Search for: All records

Tuning solubility and mechanical activation alters the stereoselectivity of the [2 + 2] photochemical cycloaddition of acenaphthylene. Photomechanochemical conditions produce the syn cyclobutane, whereas the solid-state reaction in the absence of mechanical activation provides the anti . When the photochemical dimerization occurs in a solubilizing organic solvent, there is no selectivity. Dimerization in H 2 O, in which acenaphthylene is insoluble, provides the anti product. DFT calculations reveal that insoluble and solid-state reactions proceed via a covalently bonded excimer, which drives anti selectivity. Alternatively, the noncovalently bound syn conformer is more mechanosusceptible than the anti , meaning it experiences greater destabilization, thereby producing the syn product under photomechanochemical conditions. Cyclobutanes are important components of biologically active natural products and organic materials, and we demonstrate stereoselective methods for obtaining syn or anti cyclobutanes under mild conditions and without organic solvents. With this work, we validate photomechanochemistry as a viable new direction for the preparation of complex organic scaffolds. 

The device concept of ferroelectric-based negative capacitance (NC) transistors offers a promising route for achieving energy-efficient logic applications that can outperform the conventional semiconductor technology, while viable operation mechanisms remain a central topic of debate. In this work, we report steep slope switching in MoS₂transistors back-gated by single-layer polycrystalline PbZr_0.35Ti_0.65O₃. The devices exhibit current switching ratios up to 8 × 10⁶within an ultra-low gate voltage window of$$V_{{{\mathrm{g}}}} = \pm \! 0.5$$$V_g=\pm 0.5$V and subthreshold swing (SS) as low as 9.7 mV decade⁻¹at room temperature, transcending the 60 mV decade⁻¹Boltzmann limit without involving additional dielectric layers. Theoretical modeling reveals the dominant role of the metastable polar states within domain walls in enabling the NC mode, which is corroborated by the relation between SS and domain wall density. Our findings shed light on a hysteresis-free mechanism for NC operation, providing a simple yet effective material strategy for developing low-power 2D nanoelectronics.

 

The inability to process many covalent organic frameworks (COFs) as thin films plagues their widespread utilization. Herein, a vapor‐phase pathway for the bottom‐up synthesis of a class of porphyrin‐based COFs is presented. This approach allows integrating electrocatalysts made of metal‐ion‐containing COFs into the electrodes’ architectures in a single‐step synthesis and deposition. By precisely controlling the metal sites at the atomic level, remarkable electrocatalytic performance is achieved, resulting in unprecedentedly high mass activity values. How the choice of metal atoms, i.e., cobalt and copper, can determine the catalytic activities of POR‐COFs is demonstrated. The theoretical data proves that the Cu site is highly active for nitrate conversion to ammonia on the synthesized COFs.