Visible‐light photocatalysis is a rapidly developing and powerful strategy to initiate organic transformations, as it closely adheres to the tenants of green and sustainable chemistry. Generally, ...most visible‐light‐induced photochemical reactions occur through single‐electron transfer (SET) pathways. Recently, visible‐light‐induced energy‐transfer (EnT) reactions have received considerable attentions from the synthetic community as this strategy provides a distinct reaction pathway, and remarkable achievements have been made in this field. In this Review, we highlight the most recent advances in visible‐light‐induced EnT reactions.
Making light of synthesis: The distinctive reaction pathways provided by visible‐light‐induced energy transfer (EnT) has resulted in it receiving considerable attention. This Review discusses the most recent advances in visible‐light‐induced EnT reactions.
Visible‐light‐induced photocatalytic decarboxylative alkynylations of carboxylic acids have been developed for the first time. The reaction features extremely mild conditions, broad substrate scope, ...and avoids additional oxidants. Importantly, a decarboxylative carbonylative alkynylation has also been carried out in the presence of carbon monoxide (CO) under photocatalytic conditions, which affords valuable ynones in high yields at room temperature.
Readily available carboxylic acids can easily undergo decarboxylative alkynylation/carbonylative alkynylation under visible‐light photoredox catalysis to afford a variety of versatile alkynes and ynones in good to excellent yields. These transformations feature mild conditions and a broad substrate scope.
Liquid organic hydrogen carriers (LOHCs) are powerful systems for the efficient unloading and loading molecular hydrogen. Herein, a liquid‐to‐liquid organic hydrogen carrier system based on ...reversible dehydrogenative coupling of ethylene glycol (EG) with ethanol catalysed by ruthenium pincer complexes is reported. Noticeable advantages of the current LOHC system is that both reactants (hydrogen‐rich components) and the produced esters (hydrogen‐lean components) are liquids at room temperature, and the dehydrogenation process can be performed under solvent and base‐free conditions. Moreover, the hydrogenation reaction proceeds under low hydrogen pressure (5 bar), and the LOHC system has a relatively high theoretical gravimetric hydrogen storage capacity (HSC>5.0 wt %), presenting an attractive hydrogen storage system.
Hydrogen carriers: A liquid‐to‐liquid organic hydrogen carrier system based on reversible dehydrogenation and hydrogenation reactions by using ethylene glycol and ethanol is reported. Both the reactants are abundant, cheap, and non‐toxic industrial raw materials. Moreover, this dehydrogenative esterification, as well as hydrogenation, can be conducted under base‐ and solvent‐free conditions, thus offering a promising approach for application in hydrogen storage.
A sustainable, new synthesis of oxalamides, by acceptorless dehydrogenative coupling of ethylene glycol with amines, generating H
2
, homogeneously catalyzed by a ruthenium pincer complex, is ...presented. The reverse hydrogenation reaction is also accomplished using the same catalyst. A plausible reaction mechanism is proposed based on stoichiometric reactions, NMR studies, X-ray crystallography as well as observation of plausible intermediates.
Ruthenium catalyzed acceptorless dehydrogenative coupling of ethylene glycol and amines to oxalamides is reported. The reverse hydrogenation reaction is also accomplished.
A novel visible-light-responsive chiral ligand has been developed by grafting a triplet state photosensitizer to chiral bisoxazoline ligands. Complexation of this ligand with Ni(acac)2 results in a ...powerful catalyst for the asymmetric oxidation reaction of β-ketoesters, which uses oxygen or air as the green oxidant and visible light or sunlight as the ideal driving force. Using this protocol, products containing the α-hydroxy-β-dicarbonyl motif are produced in high yields and with excellent enantiopurities.
The first asymmetric propargylic radical cyanation was realized through a dual photoredox and copper catalysis. An organic photocatalyst serves to both generate propargyl radicals and oxidize Cu(I) ...species to Cu(II) species. A chiral Cu complex functions as an efficient organometallic catalyst to resemble the propargyl radical and cyanide in an enantio-controlled manner. Thus, a diverse range of optically active propargyl cyanides were produced with high reaction efficiency and enantioselectivities (28 examples, 57–97% yields and 83–98% ee). Moreover, mechanistic investigations including experiments and density functional theory calculations were performed to illustrate on the reaction pathway and stereochemical results.
Photon loss in optical fibers prevents long-distance distribution of quantum information on the ground. Quantum repeater is proposed to overcome this problem, but the communication distance is still ...limited so far because of the system complexity of the quantum repeater scheme. Alternative solutions include transportable quantum memory and quantum-memory-equipped satellites, where long-lived optical quantum memories are the key components to realize global quantum communication. However, the longest storage time of the optical memories demonstrated so far is approximately 1 minute. Here, by employing a zero-first-order-Zeeman magnetic field and dynamical decoupling to protect the spin coherence in a solid, we demonstrate coherent storage of light in an atomic frequency comb memory over 1 hour, leading to a promising future for large-scale quantum communication based on long-lived solid-state quantum memories.
Glycolic acid is a useful and important α‐hydroxy acid that has broad applications. Herein, the homogeneous ruthenium catalyzed reforming of aqueous ethylene glycol to generate glycolic acid as well ...as pure hydrogen gas, without concomitant CO2 emission, is reported. This approach provides a clean and sustainable direction to glycolic acid and hydrogen, based on inexpensive, readily available, and renewable ethylene glycol using 0.5 mol % of catalyst. In‐depth mechanistic experimental and computational studies highlight key aspects of the PNNH‐ligand framework involved in this transformation.
A homogeneous ruthenium‐catalyzed reforming of aqueous ethylene glycol to glycolic acid and hydrogen is described. A plausible reaction mechanism, involving metal–ligand cooperation is proposed and supported by stoichiometric reactions, NMR studies, X‐ray crystallography and computational studies.
Exotic massless fermionic excitations with nonzero Berry flux, other than the Dirac and Weyl fermions, could exist in condensed matter systems under the protection of crystalline symmetries, such as ...spin-1 excitations with threefold degeneracy and spin-3/2 Rarita-Schwinger-Weyl fermions. Herein, by using the ab initio density functional theory, we show that these unconventional quasiparticles coexist with type-I and type-II Weyl fermions in a family of transition metal silicides, including CoSi, RhSi, RhGe, and CoGe, when spin-orbit coupling is considered. Their nontrivial topology results in a series of extensive Fermi arcs connecting projections of these bulk excitations on the side surface, which is confirmed by (001) surface electronic spectra of CoSi. In addition, these stable arc states exist within a wide energy window around the Fermi level, which makes them readily accessible in angle-resolved photoemission spectroscopy measurements.
This paper aims to promote the integration of animation design and cultural and creative industries. The shape gradient algorithm is used to analyze the features of the animated shapes. The ...corresponding interval distance of anime shapes is determined by calculating the curve sampling points of anime feature points. The deformation framework is created, and a sequence of anime shapes is generated using the linear interpolation method. In the deformation of anime design, the role of three algorithms, namely image segmentation module, association map of attributes, and mathematical description of EMD, on its generation is focused on the analysis. The results show that anime users from post-00 and post-10 are more inclined to anime peripherals, accounting for 30% and 35%, respectively. The annual growth rate of anime peripheral is 90.2%, and the annual growth rate of the overseas anime market is also gradually increasing, reaching a growth rate of 103.1%. A successful anime IP will certainly influence the development of its anime and cultural creation industry. The research in this paper is conducive to promoting better integration of animation design and cultural and creative industries and promoting the development of an innovation economy.
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