Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequenc...Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.展开更多
Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal co...Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal coordination has emerged as a robust methodology for chirality induction in many systems.In this work,we engineered two rigid and flexible chiral organic ligands(L_(1) and L_(2))by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties.They demonstrate versatile coordination capabilities toward both 3d-and 4f-block metals,enabling modulation of luminescent characteristics with blue,green and red emissions.Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L_(1)/L_(2) with Zn^(2+),Eu^(3+),and Tb^(3+).The coordination processes effectively rigidify molecular conformations,leading to an enhanced CPL performance.Particularly,the Tb-L_(2) complex displays superior lanthanide-centered emission with a fluorescence quantum yield of~55%and an emission dissymmetry factor glum=5.5×10^(-3).By engineering the substitution on pillar[5]arene scaffolds,we have established a metal-coordination platform with CPL characteristics,which paves the way in the design of new metal-based luminescent materials.展开更多
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for...Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.展开更多
Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin de...Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.展开更多
Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes ...Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-vip properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.展开更多
Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process...Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.展开更多
Para-quinols(p-quinols)are a kind of cyclohexa-2,5-dienones,and are widely used as active synthons in organic synthesis,medicinal chemistry and materials science.Herein,the efficient synthesis of poly-substituted aren...Para-quinols(p-quinols)are a kind of cyclohexa-2,5-dienones,and are widely used as active synthons in organic synthesis,medicinal chemistry and materials science.Herein,the efficient synthesis of poly-substituted arenes and fused cyclic compounds from p-quinols has been summarized.The mecha-nisms and the key driving force of these efficient transformations have been discussed.展开更多
Reported here is the comprehensive investigation on the formation of biphen[n]arenes by tailoring reac-tion modules.Five new macrocyclic arenes and four oligomers were synthesized by the condensation of monomers posse...Reported here is the comprehensive investigation on the formation of biphen[n]arenes by tailoring reac-tion modules.Five new macrocyclic arenes and four oligomers were synthesized by the condensation of monomers possessing different multimethoxyphenyl reaction modules and paraformaldehyde.We proved that the number and sites of methoxy on reaction modules greatly affected the reaction activity,shape,and connection mode of macrocycles.Moreover,the triangular and saddle-shaped configuration of macro-cycles were revealed by single crystal structures.The results provided a typical and fundamental guidance in designing new macrocyclic arenes.展开更多
Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herei...Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herein were fully confirmed by 1 H NMR.ES1-MS and elemental analysis.展开更多
Pillar[n]arenes primarily comprise pillar[5]arenes and pillar[6]arenes, which belong to the new class of supramolecular macrocyclic hosts. Pillar[n]arenes have aroused wide attention because of their highly rigid and ...Pillar[n]arenes primarily comprise pillar[5]arenes and pillar[6]arenes, which belong to the new class of supramolecular macrocyclic hosts. Pillar[n]arenes have aroused wide attention because of their highly rigid and symmetrical architectures, controllable cavity size, and wide applications in a wide variety of areas. Although pillar[6]arene is difficult to synthesize, numerous studies have been conducted on it. In this review, the strategies to synthesize and functionalize pillar[6]arenes are investigated systematically.In addition, their host-vip properties in organic solvents and in aqueous solution are described. Moreover, pillar[6]arenes applied in different fields(e.g., molecular recognition, drug release, cancer therapy,and gas separation) are clarified. Hopefully, this study is capable of arousing more attention from increasing scientists to study large-cavity pillar[n]arenes.展开更多
Pillar[n]arenes are a new kind of supramolecular macrocyclic hosts which have developed rapidly due to their unique topology and high functionality, giving rise to many applications in the construction of interesting ...Pillar[n]arenes are a new kind of supramolecular macrocyclic hosts which have developed rapidly due to their unique topology and high functionality, giving rise to many applications in the construction of interesting and functional materials. Among them, water-soluble pillar[n]arenes bearing triethylene oxide (TEO) chains have drawn increasing research interest due to their advantageous properties. In this review, we summarized the recent progress of dynamic materials fabricated from water soluble pillar[n]arenes bearing TEO groups, including thermo responsive materials with lower critical solution temperature (LCST) behavior, cyclic host liquids, and smart windows. It is anticipated that more and more ‘smart' supramolecular materials based on modified pillar[n]arenes will be developed in this burgeoning area of research.展开更多
Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, eas...Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, easy workup, high yield, and easily available catalyst are important features of this method.展开更多
Lignin is a renewable carbon resource to produce arenes due to its abundant aromatic structures.For the liquid-phase hydrodeoxygenation(HDO)based on metallic catalysts,the preservation of aromatic rings in lignin or i...Lignin is a renewable carbon resource to produce arenes due to its abundant aromatic structures.For the liquid-phase hydrodeoxygenation(HDO)based on metallic catalysts,the preservation of aromatic rings in lignin or its derivatives remains a challenge.Herein,we synthesized Mndoped Cu/Al_(2)O_(3) catalysts from layered double hydroxides(LDHs)for liquid-phase HDO of lignin-derived anisole.Mn doping significantly enhanced the selective deoxygenation of anisole to arenes and inhibited the saturated hydrogenation on Cu/Al_(2)O_(3).With Mn doping increasing,the surface of Cu particles was modified with MnO_(x) along with enhanced generation of oxygen vacancies(Ov).The evolution of active sites structure led to a controllable adsorption geometry of anisole,which was beneficial for increasing arenes selectivity.As a result,the arenes selectivity obtained on 4Cu/8Mn4AlO_(x) was increased to be more than 6 folds of that value on 4Cu/4Al_(2)O_(3) over the synergistic sites between metal Cu and Ov generated on MnO_(x).展开更多
（6-Amino-2-chloro-3-fluorophenyl）methanol is prepared through both traditional methods and palladium catalyzed iterative C–H halogenation reactions.In comparison to traditional approach,the C–H functionalization s...（6-Amino-2-chloro-3-fluorophenyl）methanol is prepared through both traditional methods and palladium catalyzed iterative C–H halogenation reactions.In comparison to traditional approach,the C–H functionalization strategy demonstrated a few advantages including milder reaction conditions higher yields,better selectivity and practicality,and high chemical diversity.展开更多
An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mi...An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.展开更多
The 1,3-distally selective functionalization of calix[4]arenes with benzylicbromides at the lower rim in excellent ytelds is described. The calix[4]arenes withdendritic fragnents obtalned exist in cone conformation.
A novel series of pyrimidinylthiaalkoxycalix[4]arenes with the reaction between 4,6-dimethylpyrimidine-2-thiol and the different dibromides calix[4]aryl groups have been synthesized and structurally characterized by I...A novel series of pyrimidinylthiaalkoxycalix[4]arenes with the reaction between 4,6-dimethylpyrimidine-2-thiol and the different dibromides calix[4]aryl groups have been synthesized and structurally characterized by IR, 1H NMR and MS. From their analysis data, it was found that compounds 8, 9, 11 adopted a cone conformation, while compound 10 existed as a mixture of conformations.展开更多
The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with tho...The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.展开更多
基金Financial support from Science and Technology Innovation Program of Hunan Province(No.2022RC4044)。
文摘Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金supported by the Beijing Natural Science Foundation(No.2232024)the Analysis&Testing Centre at Beijing Institute of Technology for advanced facilities.
文摘Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal coordination has emerged as a robust methodology for chirality induction in many systems.In this work,we engineered two rigid and flexible chiral organic ligands(L_(1) and L_(2))by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties.They demonstrate versatile coordination capabilities toward both 3d-and 4f-block metals,enabling modulation of luminescent characteristics with blue,green and red emissions.Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L_(1)/L_(2) with Zn^(2+),Eu^(3+),and Tb^(3+).The coordination processes effectively rigidify molecular conformations,leading to an enhanced CPL performance.Particularly,the Tb-L_(2) complex displays superior lanthanide-centered emission with a fluorescence quantum yield of~55%and an emission dissymmetry factor glum=5.5×10^(-3).By engineering the substitution on pillar[5]arene scaffolds,we have established a metal-coordination platform with CPL characteristics,which paves the way in the design of new metal-based luminescent materials.
基金supported by the fundamental research funds of Zhejiang Sci-Tech University(No.22212286-Y)the Natural Science Foundation of Zhejiang Province(No.LQ24B040003)。
文摘Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.
文摘Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.
基金the National Natural Science Foundation of China(No.22101043)the Fundamental Research Funds for the Central Universities(No.N2205013)and Northeastern University for financial support.
文摘Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-vip properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.
基金Financial support from National Key R&D Program of China(No.2022YFA1503200)National Natural Science Foundation of China(No.22188101)+1 种基金the Fundamental Research Funds for the Central Universities(No.63223007)Frontiers Science Center for New Organic Matter,Nankai University(No.63181206)and Nankai University.
文摘Herein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities,such as free carboxylic acid, aldehyde, halogen(including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp^(3))–H bonds,and short-lived reactive intermediates(aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode(BUME) with nano-electrospray ionization mass spectrometry.
基金supported by the Department of Science and Technology of Jilin Province(20220402046GH,20220101066JC).
文摘Para-quinols(p-quinols)are a kind of cyclohexa-2,5-dienones,and are widely used as active synthons in organic synthesis,medicinal chemistry and materials science.Herein,the efficient synthesis of poly-substituted arenes and fused cyclic compounds from p-quinols has been summarized.The mecha-nisms and the key driving force of these efficient transformations have been discussed.
基金the National Natural Science Foundation of China (Nos. 21971192 and 21772118)the Natural Science Foundation of Tianjin City (No. 20JCZDJC00200)
文摘Reported here is the comprehensive investigation on the formation of biphen[n]arenes by tailoring reac-tion modules.Five new macrocyclic arenes and four oligomers were synthesized by the condensation of monomers possessing different multimethoxyphenyl reaction modules and paraformaldehyde.We proved that the number and sites of methoxy on reaction modules greatly affected the reaction activity,shape,and connection mode of macrocycles.Moreover,the triangular and saddle-shaped configuration of macro-cycles were revealed by single crystal structures.The results provided a typical and fundamental guidance in designing new macrocyclic arenes.
基金supported by the National Natural Science Foundation of China(Nos.21072072 and 21102051)PCSIRT(No.IRTO953)+1 种基金Program for New Century Excellent Talent in University(No.NCET-10-0428)Self-determined Research Funds of CCNU from the Colleges Basic Research and Operation of MOE (Nos.CCNU11C01002,CCNU12A01004 and CCNU12A02012)
文摘Several water-soluble calix[4]arenes were synthesized via radical addition reaction between thiols and alkenes under UV lamp irradiation（λ= 365 nm） in good yields.The structures of these compounds synthesized herein were fully confirmed by 1 H NMR.ES1-MS and elemental analysis.
基金supported by the National Natural Science Foundation of China(No.22007052)the Natural Science Foundation of Jiangsu Province(No.BK20190917)+2 种基金the project of“Six Talent Peaks in Jiangsu Province”(No.XCL-085)Science and Technology Project of Nantong City(No.JC2020055)China Postdoctoral Science Foundation(No.2020M680071)。
文摘Pillar[n]arenes primarily comprise pillar[5]arenes and pillar[6]arenes, which belong to the new class of supramolecular macrocyclic hosts. Pillar[n]arenes have aroused wide attention because of their highly rigid and symmetrical architectures, controllable cavity size, and wide applications in a wide variety of areas. Although pillar[6]arene is difficult to synthesize, numerous studies have been conducted on it. In this review, the strategies to synthesize and functionalize pillar[6]arenes are investigated systematically.In addition, their host-vip properties in organic solvents and in aqueous solution are described. Moreover, pillar[6]arenes applied in different fields(e.g., molecular recognition, drug release, cancer therapy,and gas separation) are clarified. Hopefully, this study is capable of arousing more attention from increasing scientists to study large-cavity pillar[n]arenes.
基金financial support from the National Natural Science Foundation of China(No. 21702020)and Maynooth University
文摘Pillar[n]arenes are a new kind of supramolecular macrocyclic hosts which have developed rapidly due to their unique topology and high functionality, giving rise to many applications in the construction of interesting and functional materials. Among them, water-soluble pillar[n]arenes bearing triethylene oxide (TEO) chains have drawn increasing research interest due to their advantageous properties. In this review, we summarized the recent progress of dynamic materials fabricated from water soluble pillar[n]arenes bearing TEO groups, including thermo responsive materials with lower critical solution temperature (LCST) behavior, cyclic host liquids, and smart windows. It is anticipated that more and more ‘smart' supramolecular materials based on modified pillar[n]arenes will be developed in this burgeoning area of research.
文摘Synthesis of symmetrical diaryl sulfoxides from arenes and thionyl chloride in the presence of a catalytic amount of iodine at room temperature under solvent-free conditions is described. Mild reaction conditions, easy workup, high yield, and easily available catalyst are important features of this method.
基金supported by National Natural Science Foundation of China (21938008).
文摘Lignin is a renewable carbon resource to produce arenes due to its abundant aromatic structures.For the liquid-phase hydrodeoxygenation(HDO)based on metallic catalysts,the preservation of aromatic rings in lignin or its derivatives remains a challenge.Herein,we synthesized Mndoped Cu/Al_(2)O_(3) catalysts from layered double hydroxides(LDHs)for liquid-phase HDO of lignin-derived anisole.Mn doping significantly enhanced the selective deoxygenation of anisole to arenes and inhibited the saturated hydrogenation on Cu/Al_(2)O_(3).With Mn doping increasing,the surface of Cu particles was modified with MnO_(x) along with enhanced generation of oxygen vacancies(Ov).The evolution of active sites structure led to a controllable adsorption geometry of anisole,which was beneficial for increasing arenes selectivity.As a result,the arenes selectivity obtained on 4Cu/8Mn4AlO_(x) was increased to be more than 6 folds of that value on 4Cu/4Al_(2)O_(3) over the synergistic sites between metal Cu and Ov generated on MnO_(x).
基金supported by ‘973’ Project (No. 2011CB965300)NSFC (Nos. 21142008, 21302106)+1 种基金Tsinghua University 985 Phase II Fundsthe Tsinghua University Initiative Scientific Research Program
文摘（6-Amino-2-chloro-3-fluorophenyl）methanol is prepared through both traditional methods and palladium catalyzed iterative C–H halogenation reactions.In comparison to traditional approach,the C–H functionalization strategy demonstrated a few advantages including milder reaction conditions higher yields,better selectivity and practicality,and high chemical diversity.
文摘An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.
文摘The 1,3-distally selective functionalization of calix[4]arenes with benzylicbromides at the lower rim in excellent ytelds is described. The calix[4]arenes withdendritic fragnents obtalned exist in cone conformation.
基金the National Natural Science Foundation of China （No. 20376059）.
文摘A novel series of pyrimidinylthiaalkoxycalix[4]arenes with the reaction between 4,6-dimethylpyrimidine-2-thiol and the different dibromides calix[4]aryl groups have been synthesized and structurally characterized by IR, 1H NMR and MS. From their analysis data, it was found that compounds 8, 9, 11 adopted a cone conformation, while compound 10 existed as a mixture of conformations.
文摘The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.
