The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the singl...The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.展开更多
Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persis...Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persistent challenge.This challenge has spurred the exploration of efficient activation methods to overcome this issue.In recent years,photocatalysis has emerged as a mild and potent tool for the single electron reduction of unactivated alkyl chlorides,opening up new possibilities in this field.Considering the rapid advancements in this area,a comprehensive review that provides a conceptual understanding of this emerging field,with a specific focus on reaction design and catalytic mechanisms,would be timely and highly valuable.Hence,we present an overview of various synthetic techniques for photoinduced single electron reduction of unactivated alkyl chlorides.Furthermore,we also discuss the limitations of the present methods and future directions that lie ahead in this field.展开更多
We propose a novel analytical model to describe the drain-source current as well as gate-source of single-electron transistors (SETs) at high temperature. Our model consists on summing the tunnel current and thermioni...We propose a novel analytical model to describe the drain-source current as well as gate-source of single-electron transistors (SETs) at high temperature. Our model consists on summing the tunnel current and thermionic contribution. This model will be compared with another model.展开更多
Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was...Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.展开更多
Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of the...Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of them were isolated as stable crystals and studied by single-crystal X-ray diffraction,superconducting quantum interference device measurements,electron paramagnetic resonance,nuclear magnetic resonance,and UV–vis spectroscopy.Antiferromagnetic exchange coupling was observed among both 3 and 4.Radical anion and cation are basically separated in 3,while 4 featured a relatively strong anion-cationπ–πstacking interaction.This work demonstrated that the Lewis acid coupled electron transfer is an efficient way to prepare stable radical ion pairs.展开更多
The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.H...The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.展开更多
Photocatalytic carbon dioxide(CO_(2))to carbon monoxide(CO)offers a promising way for both alleviating the greenhouse effect and meeting the industrial demand.Herein,we constructed a Co single-atom catalyst with inten...Photocatalytic carbon dioxide(CO_(2))to carbon monoxide(CO)offers a promising way for both alleviating the greenhouse effect and meeting the industrial demand.Herein,we constructed a Co single-atom catalyst with intentional low-coordination environment design on porous ZnO(denoted as Co1/ZnO).Impressively,Co1/ZnO exhibited a remarkable activity with a CO yield rate of 22.25 mmol·g^(-1)·h^(-1) and a selectivity of 80.2%for CO_(2) photoreduction reactions under visible light.The incorporation of single Co atoms provided an additional photo-generated electron transfer channel,which suppressed the carrier recombination of photocatalysts.Moreover,the unsaturated Co active sites were capable to adsorb CO_(2) molecule spontaneously,thus facilitating the activation of CO_(2) molecule during CO_(2) reduction course.展开更多
文摘The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.
基金supported by the National Natural Science Foundation of China (22001248)the Fundamental Research Funds for the Central Universitiesthe University of the Chinese Academy of Sciences。
文摘Alkyl chlorides are abundant and easily accessible starting materials.However,due to the high reduction potentials associated with unactivated alkyl chlorides,achieving their single electron reduction remains a persistent challenge.This challenge has spurred the exploration of efficient activation methods to overcome this issue.In recent years,photocatalysis has emerged as a mild and potent tool for the single electron reduction of unactivated alkyl chlorides,opening up new possibilities in this field.Considering the rapid advancements in this area,a comprehensive review that provides a conceptual understanding of this emerging field,with a specific focus on reaction design and catalytic mechanisms,would be timely and highly valuable.Hence,we present an overview of various synthetic techniques for photoinduced single electron reduction of unactivated alkyl chlorides.Furthermore,we also discuss the limitations of the present methods and future directions that lie ahead in this field.
文摘We propose a novel analytical model to describe the drain-source current as well as gate-source of single-electron transistors (SETs) at high temperature. Our model consists on summing the tunnel current and thermionic contribution. This model will be compared with another model.
基金Supported by Project of Education Department of Liaoning Province(20040084)
文摘Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.
基金the National Key R&D Program of China(grant no.2018YFA0306004)the National Natural Science Foundation of China(grant no.21525102)for their financial support.
文摘Single electron transition reactions between amines(Lewis base)and B(C_(6)F_(5))_(3)(Lewis acid)in cooperation with benzoquinones gave rise to a frustrated radical pair 3 and a nonfrustrated radical pair 4.Both of them were isolated as stable crystals and studied by single-crystal X-ray diffraction,superconducting quantum interference device measurements,electron paramagnetic resonance,nuclear magnetic resonance,and UV–vis spectroscopy.Antiferromagnetic exchange coupling was observed among both 3 and 4.Radical anion and cation are basically separated in 3,while 4 featured a relatively strong anion-cationπ–πstacking interaction.This work demonstrated that the Lewis acid coupled electron transfer is an efficient way to prepare stable radical ion pairs.
基金financially supported by the National Natural Science Foundation of China(Nos.92061110,21925303,21829501,21771186,21222301,21528303,and 21171170)the Anhui Provincial Natural Science Foundation(2108085Y05 and 2108085MB56)+1 种基金Collaborative Innovation Program of Hefei Science Center,CAS(Nos.2020HSCCIP005 and 2022HSC-CIP018)the Hefei National Laboratory for Physical Sciences at the Microscale(KF2020102).
文摘The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.
基金supported by the National Natural Science Foundation of China(Nos.1222508,U1932213)the Fundamental Research Funds for the Central Universities(No.WK2060000016)+1 种基金the USTC Research Funds of the Double First-Class Initiative(No.YD2310002005)the Youth Innovation Promotion Association CAS(No.2020454)。
文摘Photocatalytic carbon dioxide(CO_(2))to carbon monoxide(CO)offers a promising way for both alleviating the greenhouse effect and meeting the industrial demand.Herein,we constructed a Co single-atom catalyst with intentional low-coordination environment design on porous ZnO(denoted as Co1/ZnO).Impressively,Co1/ZnO exhibited a remarkable activity with a CO yield rate of 22.25 mmol·g^(-1)·h^(-1) and a selectivity of 80.2%for CO_(2) photoreduction reactions under visible light.The incorporation of single Co atoms provided an additional photo-generated electron transfer channel,which suppressed the carrier recombination of photocatalysts.Moreover,the unsaturated Co active sites were capable to adsorb CO_(2) molecule spontaneously,thus facilitating the activation of CO_(2) molecule during CO_(2) reduction course.
