The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of th...The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.展开更多
The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[c...The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[cyclo- hexane-1,2′-indene]-1′,4（3′H）-dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields （up to 99%）. This catalytic system was also extended to the double Michael reaction of less reactive 1-indone and the desired products were also obtained in 31%-62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.展开更多
Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids...Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids in single-molecule junctions represents a cutting-edge and rapidly evolving field of research at the intersection of nanoscience,materials chemistry,and electronics.This review explores recent advances where ionic liquids function as electrolytes,dielectric layers,and structural elements within single-molecule junctions,reshaping charge transport,redox reactions,and molecular behaviors in these nanoscale systems.We comprehensively dissect fundamental concepts,techniques,and modulation mechanisms,elucidating the roles of ionic liquids as gates,electrochemical controllers,and interface components in singlemolecule junctions.Encompassing applications from functional device construction to unraveling intricate chemical reactions,this review maps the diverse applications of ionic liquids in single-molecule junctions.Moreover,we propose critical future research topics in this field,including catalysis involving ionic liquids at the single-molecule level,functionalizing single-molecule devices using ionic liquids,and probing the structure and interactions of ionic liquids.These endeavors aim to drive technological breakthroughs in nanotechnology,energy,and quantum research.展开更多
基金This work was supported by the National Natural Science Key Foundation of China (20490209) and Young Teacher Foundation of Beijing Chemical Technology University (QN0308)
文摘The geometries of reactant, product and transition state of the title reaction have been optimized by using density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/6- 311++G(d,p) levels. The variations of the bond parameters in the course of reaction were analyzed. The zero point energy corrections were performed by vibrational analysis. The equilibrium states and the transition state were verified according to the number of virtue frequency of geometry. The intrinsic reaction coordinates (IRC) were calculated from the transition state. The calculated results show that the double bond rearrangement of butene catalyzed by 1-butyl-3-methyl-imidazolium cation is a one-step reaction. The forward energy barrier of isomerization from 1-butene to 2- butene is about 193 kJ·mol-1 and the reverse energy barrier about 209 kJ·mol-1 at the B3LYP/6- 31G(d,p) level, which means that the reaction is easy to proceed at or above room temperature.
文摘The double Michael reactions between benzofuran-3-one or 1-indone and symmetric dienones in the presence of catalytic ionic liquids were successfully developed and spiro[benzofuran-2, 1′-cyclohexane]-3-one or spiro[cyclo- hexane-1,2′-indene]-1′,4（3′H）-dione derivatives containing a spiro quaternary stereogenic center, which widely exist in biologically active products and building blocks in organic synthesis, were obtained in excellent yields （up to 99%）. This catalytic system was also extended to the double Michael reaction of less reactive 1-indone and the desired products were also obtained in 31%-62% yields. The catalytic system was highly active and efficient for a broad of substrates under mild conditions.
基金primary financial supports from the National Key R&D Program of China(2021YFA1200102,2021YFA1200101,and 2022YFE0128700)the National Natural Science Foundation of China(22173050,22150013,21727806,and 21933001)+4 种基金the New Cornerstone Science Foundation through the XPLORER PRIZEthe Natural Science Foundation of Beijing(2222009)Beijing National Laboratory for Molecular Sciences(BNLMS202105)the Fundamental Research Funds for the Central Universities(63223056)“Frontiers Science Center for New Organic Matter”at Nankai University(63181206).
文摘Single-molecule junctions,integrating individual molecules as active components between electrodes,serve as fundamental building blocks for advanced electronic and sensing technologies.The application of ionic liquids in single-molecule junctions represents a cutting-edge and rapidly evolving field of research at the intersection of nanoscience,materials chemistry,and electronics.This review explores recent advances where ionic liquids function as electrolytes,dielectric layers,and structural elements within single-molecule junctions,reshaping charge transport,redox reactions,and molecular behaviors in these nanoscale systems.We comprehensively dissect fundamental concepts,techniques,and modulation mechanisms,elucidating the roles of ionic liquids as gates,electrochemical controllers,and interface components in singlemolecule junctions.Encompassing applications from functional device construction to unraveling intricate chemical reactions,this review maps the diverse applications of ionic liquids in single-molecule junctions.Moreover,we propose critical future research topics in this field,including catalysis involving ionic liquids at the single-molecule level,functionalizing single-molecule devices using ionic liquids,and probing the structure and interactions of ionic liquids.These endeavors aim to drive technological breakthroughs in nanotechnology,energy,and quantum research.
