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Barbee Erichsen posted an update 6 months ago
Here we report a unique transition-metal-free C(sp3)-H/C(sp3)-H coupling of cycloalkanes at room temperature. Unactivated cycloalkanes and 2-azaallyls underwent the combination process of single-electron transfer (SET) and hydrogen atom transfer (HAT) to deliver a wide variety of cycloalkane-functionalized products. This expedient approach enables C(sp3)-H/C(sp3)-H coupling of cycloalkanes under mild conditions without transition metals, initiators, and oxidants.Regio- and stereoselective hydrostannylation of alkyl ethynyl ethers generates alkenyl ethers, which are useful building blocks in organic synthesis. This efficient synthetic method, however, is limited. Here, we report not only an efficient method for a highly regio- and stereoselective Pd-catalyzed hydrostannylation of alkyl ethynyl ethers but also a scalable synthesis and construction of the core framework of luminamicin possessing all functional groups and stereocenters.Here we propose a new parameter, the Expanding Coefficient (EC), that can be correlated with the thermodynamic stability of supramolecular complexes governed by weak secondary interactions and obeying the induced-fit model. The EC values show a good linear relationship with the log Kapp of the respective pseudorotaxane complexes investigated. According to Cram’s Principle of Preorganization, the EC can be considered an approximate mechanical measure of the host’s reorganization energy cost upon adopting the final bound geometry.Potassium acyltrifluoroborates (KATs) are opening up new avenues in chemical biology, materials science, and synthetic organic chemistry due to their intriguing reactivities. However, the synthesis of these compounds remains mostly complicated and time-consuming. Herein, we have developed chemoselective Pd-catalyzed approaches for the late-stage diversification of arenes bearing prefunctionalized KATs. These approaches feature chemoselective cross-coupling, rapid diversification, functional group tolerance, mild reaction conditions, simple operation, and high yields.The geometric structure of carbon electrodes affects their electrochemical behavior, and large-scale surface roughness leads to thin layer electrochemistry when analyte is trapped in pores. However, the current response is always a mixture of both thin layer and diffusion processes. Here, we systematically explore the effects of thin layer electrochemistry and diffusion at carbon fiber (CF), carbon nanospike (CNS), and carbon nanotube yarn (CNTY) electrodes. The cyclic voltammetry (CV) response to the surface-insensitive redox couple Ru(NH3)63+/2+ is tested, so the geometric structure is the only factor. At CFs, the reaction is diffusion-controlled because the surface is smooth. CNTY electrodes have gaps between nanotubes that are about 10 μm deep, comparable with the diffusion layer thickness. Selleck AM 095 CNTY electrodes show clear thin layer behavior due to trapping effects, with more symmetrical peaks and ΔEp closer to zero. CNS electrodes have submicrometer scale roughness, so their CV shape is mostly due to diffusion, not thin layer effects. However, even the 10% contribution of thin layer behavior reduces the peak separation by 30 mV, indicating ΔEp is influenced not only by electron transfer kinetics but also by surface geometry. A new simulation model is developed to quantitate the thin layer and diffusion contributions that explains the CV shape and peak separation for CNS and CNTY electrodes, providing insight on the impact of scan rate and surface structure size. Thus, this study provides key understanding of thin layer and diffusion processes at different surface structures and will enable rational design of electrodes with thin layer electrochemistry.The autodetachment dynamics of vibrational Feshbach resonances of the quadrupole-bound state (QBS) for the first time has been investigated in real time for the first excited state of the 4-cyanophenoxide (4-CP) anion. Individual vibrational resonances of the cryogenically cooled 4-CP QBS have been unambiguously identified, and their autodetachment rates state-specifically measured using the picosecond time-resolved pump-probe technique employing the photoelectron velocity-map imaging method. The autodetachment lifetime (τ) is found to be strongly dependent on mode, giving τ values of ∼56, ∼27, and ≤2.8 ps for the 12’1 (Evib = 406 cm-1), 12’2 (Evib = 806 cm-1), and 21’1 (Evib = 220 cm-1) modes, respectively. The striking mode-specific behavior of the QBS lifetime has been invoked by the physical model in which the loosely bound electron falls off by the dynamic wobbling of the three-dimensional quadrupole moment ellipsoid associated with the corresponding vibrational motion in the autodetachment process.Two-dimensional (2D) Rashba semiconductors with structure inversion asymmetry and a spin-orbit coupling (SOC) effect show promising applications in nanospintronics, such as spin field effect transistors (FETs). Here, we systematically investigate the electronic structures and Rashba effect of 2D polar perovskites ABX3 (A = Cs+ or Rb+; B = Pb2+ or Sn2+; X = Cl, Br, or I) by first-principles density functional theory calculations. We demonstrate that, except for the cubic case, 2D polar perovskites from tetragonal and orthorhombic three-dimensional (3D) bulks exhibit a strong intrinsic Rashba effect around the Γ point, due to their structure inversion asymmetry and the strong SOC effect of heavy atoms. In particular, 2D orthorhombic RbSnI3 shows the largest Rashba constant of 1.176 eV Å among these polar perovskites, which is comparable to that of 3D bulk perovskites previously reported in experiments and theory. Furthermore, several 2D polar perovskites also show a strong electric field response. In particular, 2D tetragonal RbPbI3 and tetragonal CsPbI3 have strong electric field responses of >0.5 e Å2. Therefore, 2D polar perovskites as promising Rashba semiconductors possess large Rashba constants and strong electric field responses, resulting in a short spin channel length of tens of nanometers to preserve the spin coherence in spin FETs, superior to conventional 3D micrometer spin FETs.
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