Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excel...Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.展开更多
A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,h...A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.展开更多
In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cuc...Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril(Q[10])and the smallest cucurbituril-like macrocycle(TD[4]).X-ray crystal structure analysis revealed that TD[4]was encapsulated in the cavity of Q[10]to form a 1:1 complex.Importantly,competitive vip studies suggested that TD[4]had the highest binding constant with the Q[10]host among the vips used,including Q[5],Me_(8)TD[4],and amantadine molecules in water.Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils,which expanded the family of molecular Russian dolls.展开更多
Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic s...Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic structure and modified functional groups of these macrocycles can influence substrate and transition state stability, as well as reaction selectivity. The inner cavities of these macrocycles are particularly beneficial, as they enable substrates to adopt preorganized arrangements and serve as versatile platforms for highly efficient supramolecular catalytic systems. This minireview provides an overview of recent advancements in supramolecular catalysis using various macrocycles, such as crown ethers, cyclodextrins,calixarenes, pillararenes, cucurbiturils, and other novel macrocycles.展开更多
Reported here is the synthesis of a new macrocycle bearing anionic carboxylate groups with water-soluble aggregation-induced emission(AIE).The water-soluble macrocycle without typical AIE luminogens is constructed bas...Reported here is the synthesis of a new macrocycle bearing anionic carboxylate groups with water-soluble aggregation-induced emission(AIE).The water-soluble macrocycle without typical AIE luminogens is constructed based on the building block of benzothiadiazole.It exhibits a remarkable AIE effect.This watersoluble macrocycle can selectively bind different types of biogenic amines in aqueous media with the tightest binding towards spermine.The fluorescence enhancement induced by supramolecular encapsulation is used to detect spermine.展开更多
The topology of conjugated macrocycles had significant impacts on their photo-physical and photochemical properties.Herein,a series ofπ-conjugated macrocycles with diverse topology were synthesized via intramolecular...The topology of conjugated macrocycles had significant impacts on their photo-physical and photochemical properties.Herein,a series ofπ-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling.Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR,MALDI-TOF mass spectra,crystal analysis and scanning tunneling microscopy(STM).Depending on the structural topology and structural rigidity,these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state.Monocyclic phenylene vinylene macrocycle(denoted as MST)exhibiting aggregation-induced emission behavior,was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photodimerization due to lower strain and more flourishing intramolecular motions.After UV light irradiation,relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation.By contrast,highly constrained bicyclic analogue(named as DMTPE)with central tetraphenylethene core,displayed high emission quantum yields of 68%both in solution and in the solid state,and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved[2+2]photo-dimerization.Based on the solution-mediated photo-polymerization of MST moiety,multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.展开更多
Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments....Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments.By mimicking the cavity feature of bioreceptors,Prof.Wei Jiang proposed and clarified the concept of“endo-functionalized cavity”.Through situating polar binding sites into a deep hydrophobic cavity,we designed and synthesized several macrocyclic hosts,among which amide naphthotubes are the most representative.The hosts can selectively recognize various polar molecules including organic micropollutants,drug molecules,and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding.In addition,these biomimetic hosts have been applied in spectroscopic analysis,adsorptive separation and self-assembly.In this review,we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group.We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.展开更多
Artificial macrocycle with high binding selectivity in water is often challenging but urgently needed in various research and application areas.Herein,we report a new water-soluble biomimetic tetralactam macrocycle an...Artificial macrocycle with high binding selectivity in water is often challenging but urgently needed in various research and application areas.Herein,we report a new water-soluble biomimetic tetralactam macrocycle and realize the ultra-high selectivity to nucleosides over corresponding monophosphate nucleotides by rational modification.The introduction of charged groups at the periphery of endofunctionalized cavity makes the selectivity(guanosine to guanosine 5-monophosphate)increase remarkably from 100 to 1119.Based on the ultra-high selectivity of biomimetic tetralactam macrocycle,the sensitive CD73 enzyme activity assay was then achieved through product-selective fluorescence indicator displacement assay.Furthermore,the capability of the proposed method for inhibitor screening was successfully displayed.展开更多
Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable...Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable1H NMR spectra suggested formation of robust and discrete structures in solution.X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state,which was formed from[4+8]condensation of the two reactants via 16 imine bonds.DFT calculations discovered that only the[4+8]twisted product is thermodynamically favorable,which accounts for its highly selective and efficient formation out of a library of many other combinations.展开更多
Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their ...Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.展开更多
Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PF...Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PFOS in water. In this study, a tetraphenylethylene-derived macrocycle Bowtie Cyclophane has been developed as a fluorescent sensor based on aggregation-induced emission enhancement and fluorochromism. Sensitive detection of PFOS has been achieved with a limit of detection(LOD) of47.3 ± 2.0 nmol/L(25.4 ± 1.1 μg/L) accompanied by visual fluorescence color changes.展开更多
Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydrox...Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.展开更多
Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors...Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.展开更多
The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, ...The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?展开更多
A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b ...A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.展开更多
The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling ...The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.展开更多
Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we ...Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we summarize the recent research progress on the synthesis and assembly of AuNPs functionalized with different supramolecular macrocyclic compounds, i.e., crown ethers, cyclophanes, cyclodextrins （CDs）, cucurbit[n]urils （CB[n]）, calix[n]arenes, and pillar[n]arenes （PIn]A）. Meanwhile, applications of these supramolecular hybrid nanomaterials in the fields of sensors, biomedicine and plasmonic devices are also presented.展开更多
The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been...The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been described to reveal the utility of halogen bonding in inducing the formation of supramolecular macrocycles.All the three compounds formed intermolecular I···N halogen bonding.For short compound 1,halogen bonding induced the formation of an extended supramolecular array.For longer folded compounds 2 and 3,halogen bonding could hold two molecules to form supramolecular macrocycles even by adopting a highly distorted,energetically less favorable conformation(for 3).Depending on the solvent for the growth of crystals,compound 3 could also gave rise to a halogen bonded supramolecular double helix.展开更多
Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we repor...Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we report a novel macrocycle WreathArene,a fluorinated C;-symmetrical [1;]-paracyclophane.In the crysalline state,WreathArene features vip-adaptive polymorphism for polyhaloalkanes including chloroform,tribromomethane,1,1,2-trichloroethane,and 1,2-dibromoethane.Non-covalent C-halogen…πinteractions are observed in all of these host-vip structures.Based on these properties,the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.展开更多
基金the National Natural Science Foundation of China(No.22271154)the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078).
文摘Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.
基金supported by the National Natural Science Foundation of China(No.22271202 to L.Yuan,No.22201193 to X.Li)the Sichuan Science and Technology Program(No.2023NSFSC0109 to X.Li)+2 种基金the Fundamental Research Funds for the Central Universities and the Hundred Talent Program of Sichuan University(No.YJ2021158 to X.Li)Sichuan University Interdisciplinary Innovation Fund(X.Li)Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.SKLSSM2024037)。
文摘A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
基金supported by the National Natural Science Foundation of China(No.2271090)。
文摘Host-vip recognition-based macrocycle in macrocycle to form"Russian doll"assemblies remains an interesting topic in supramolecular chemistry.Herein,a macrocycle-in-macrocycle assembly was studied using cucurbit[10]uril(Q[10])and the smallest cucurbituril-like macrocycle(TD[4]).X-ray crystal structure analysis revealed that TD[4]was encapsulated in the cavity of Q[10]to form a 1:1 complex.Importantly,competitive vip studies suggested that TD[4]had the highest binding constant with the Q[10]host among the vips used,including Q[5],Me_(8)TD[4],and amantadine molecules in water.Our results provided a new cucurbituril-based Russian-doll structure containing both the largest and smallest cavities of the cucurbiturils,which expanded the family of molecular Russian dolls.
基金the financial support from the Start-up Grant of Henan University of Technology (No.0004/31401509)the financial support from Distinguished University Professor grant (Nanyang Technological University)+1 种基金AcRF Tier 1 grants from the Ministry of Education of Singapore (Nos.RG107/19, RG11/20and RT14/20)the Agency for Science,Technology and Research (A*STAR) under its MTC Individual Research Grants (No.M21K2c0114)。
文摘Numerous supramolecular macrocycles have been utilized for developing catalysts by exploiting their specific molecular recognition and ability to form inclusion complexes through noncovalent interactions. The cyclic structure and modified functional groups of these macrocycles can influence substrate and transition state stability, as well as reaction selectivity. The inner cavities of these macrocycles are particularly beneficial, as they enable substrates to adopt preorganized arrangements and serve as versatile platforms for highly efficient supramolecular catalytic systems. This minireview provides an overview of recent advancements in supramolecular catalysis using various macrocycles, such as crown ethers, cyclodextrins,calixarenes, pillararenes, cucurbiturils, and other novel macrocycles.
基金the Natural Science Foundation of Zhejiang Province(Nos.LR24B020003 and LQ24B020003)the National Natural Science Foundation of China(No.21921003)for financial support。
文摘Reported here is the synthesis of a new macrocycle bearing anionic carboxylate groups with water-soluble aggregation-induced emission(AIE).The water-soluble macrocycle without typical AIE luminogens is constructed based on the building block of benzothiadiazole.It exhibits a remarkable AIE effect.This watersoluble macrocycle can selectively bind different types of biogenic amines in aqueous media with the tightest binding towards spermine.The fluorescence enhancement induced by supramolecular encapsulation is used to detect spermine.
基金supported by the National Natural Science Foundation of China(Nos.21704065,22272039)National Key Basic Research Program of China(No.2016YFA0200700)Guangdong Basic and Applied Basic Research Foundation(No.2023A1515030228)。
文摘The topology of conjugated macrocycles had significant impacts on their photo-physical and photochemical properties.Herein,a series ofπ-conjugated macrocycles with diverse topology were synthesized via intramolecular McMurry coupling.Their chemical structure and macrocyclic topology were unambiguously confirmed via NMR,MALDI-TOF mass spectra,crystal analysis and scanning tunneling microscopy(STM).Depending on the structural topology and structural rigidity,these cyclic compounds display obviously distinctive emission behavior and photochemical reactions in the solution and in the solid state.Monocyclic phenylene vinylene macrocycle(denoted as MST)exhibiting aggregation-induced emission behavior,was more vulnerable to photo-cyclization in solution and triplet sensitizer promoted photodimerization due to lower strain and more flourishing intramolecular motions.After UV light irradiation,relatively more flexible MST could yield the anti-dimer via triplet excimer on the HOPG surface confirmed by STM investigation.By contrast,highly constrained bicyclic analogue(named as DMTPE)with central tetraphenylethene core,displayed high emission quantum yields of 68%both in solution and in the solid state,and was relatively inert to photochemical reactions and yield syn-dimer on the surface via singlet excimer involved[2+2]photo-dimerization.Based on the solution-mediated photo-polymerization of MST moiety,multicyclic porous carbon-rich ribbon connected with four-membered ring was successfully constructed and validated via STM imaging.
基金the National Natural Science Foundation of China(Nos.22174059 and 22201128)Hunan Provincial Natural Science Foundation of China(Nos.2022JJ40363 and 2022JJ40365)+1 种基金the Young Science and Technology Innovation Program of Hunan Province(No.2022RC1230)China Postdoctoral Science Foundation(No.2022M721542)for financial support。
文摘Selective molecular recognition in water is routine for bioreceptors,but remains challenging for synthetic hosts.This is principally because noncovalent interactions are usually less efficient in aqueous environments.By mimicking the cavity feature of bioreceptors,Prof.Wei Jiang proposed and clarified the concept of“endo-functionalized cavity”.Through situating polar binding sites into a deep hydrophobic cavity,we designed and synthesized several macrocyclic hosts,among which amide naphthotubes are the most representative.The hosts can selectively recognize various polar molecules including organic micropollutants,drug molecules,and chiral molecules in water by employing the hydrophobic effect and shielded hydrogen bonding.In addition,these biomimetic hosts have been applied in spectroscopic analysis,adsorptive separation and self-assembly.In this review,we provide an overview of recent advances on amide naphthotubes with special emphasis on the efforts of Jiang's group.We are convinced that these biomimetic macrocycles will make further contributions to supramolecular chemistry and beyond.
基金financially supported by National Natural Science Foundation of China(Nos.22174059 and 22201128)Hunan Provincial Natural Science Foundation of China(Nos.2022JJ40363,2022JJ40365 and 2022RC1230)+1 种基金the Excellent youth funding of Hunan Provincial Education Department(No.22B0460)China Postdoctoral Science Foundation(No.2022M721542)。
文摘Artificial macrocycle with high binding selectivity in water is often challenging but urgently needed in various research and application areas.Herein,we report a new water-soluble biomimetic tetralactam macrocycle and realize the ultra-high selectivity to nucleosides over corresponding monophosphate nucleotides by rational modification.The introduction of charged groups at the periphery of endofunctionalized cavity makes the selectivity(guanosine to guanosine 5-monophosphate)increase remarkably from 100 to 1119.Based on the ultra-high selectivity of biomimetic tetralactam macrocycle,the sensitive CD73 enzyme activity assay was then achieved through product-selective fluorescence indicator displacement assay.Furthermore,the capability of the proposed method for inhibitor screening was successfully displayed.
基金supported by the National Natural Science Foundation of China(Nos.21971223 and 21772178)。
文摘Trifluoroacetic acid(TFA)catalyzed condensation reaction between tetraaminooxacalix[4]arene and N-alkylcarbazole-3,6-dicarbaldehyde in CH_(2)Cl2afforded a single product in 87%–89%yield.Well-defined yet undissolvable1H NMR spectra suggested formation of robust and discrete structures in solution.X-ray single crystal analysis further revealed a giant twisted double-layer chiral macrocycle in the solid state,which was formed from[4+8]condensation of the two reactants via 16 imine bonds.DFT calculations discovered that only the[4+8]twisted product is thermodynamically favorable,which accounts for its highly selective and efficient formation out of a library of many other combinations.
文摘Novel phosphorus-containing polyoxamacrocycles with one to two reactive thiophosphoryl chloride groups 5, 6, 7, 8 were synthesized from bishydroxyl compounds 1, 2, 3, 4 and thiophosphoryl chloride respectively. Their structures were confirmed by ^ 1H NMR, ^13C NMR, ^31p NMR and elemental analysis.
基金Financial support from the National Natural Science Foundation of China (Nos. 21672227, 21922113, 22071257)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB17000000)+2 种基金the National Key Research and Development Program of China (No. 2017YFA0206903)K.C.Wong Education Foundationthe TIPC Director’s Fund。
文摘Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PFOS in water. In this study, a tetraphenylethylene-derived macrocycle Bowtie Cyclophane has been developed as a fluorescent sensor based on aggregation-induced emission enhancement and fluorochromism. Sensitive detection of PFOS has been achieved with a limit of detection(LOD) of47.3 ± 2.0 nmol/L(25.4 ± 1.1 μg/L) accompanied by visual fluorescence color changes.
基金sponsored by Isfahan University of technology(IUT)
文摘Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.
基金the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-05-E00012)Program for Changjiang Scholars and Innovative Research Team in University for financial support+2 种基金the financial supports sponsored by NSFC/China(Nos.22071061,52003081)Shanghai Sailing Program(No.19YF1412900)Microscale Magnetic Resonance Platform of ECNU.
文摘Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.
文摘The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?
基金supported by Central China Normal University and the National Natural Science Foundation of China (20472022 and 20672042)
文摘A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.
基金supported by the National Natural Science Foundation of China (Nos. 21762028 and 21462027)Jiangxi Province Natural Science Foundation (Nos. 20161BAB213065 and 20171BAB203009)
文摘The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.
基金the National Natural Science Foundation of China(No. 21272093)the Research Fund for the Doctoral Program of Higher Education of China(No.20120061120117)the Independent Innovation Research Program from the State Key Laboratory of Supramolecular Structure and Materials for financial support
文摘Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we summarize the recent research progress on the synthesis and assembly of AuNPs functionalized with different supramolecular macrocyclic compounds, i.e., crown ethers, cyclophanes, cyclodextrins （CDs）, cucurbit[n]urils （CB[n]）, calix[n]arenes, and pillar[n]arenes （PIn]A）. Meanwhile, applications of these supramolecular hybrid nanomaterials in the fields of sensors, biomedicine and plasmonic devices are also presented.
基金the National Natural Science Foundation of China(Nos.21772026 and 21432004)for financial support
文摘The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been described to reveal the utility of halogen bonding in inducing the formation of supramolecular macrocycles.All the three compounds formed intermolecular I···N halogen bonding.For short compound 1,halogen bonding induced the formation of an extended supramolecular array.For longer folded compounds 2 and 3,halogen bonding could hold two molecules to form supramolecular macrocycles even by adopting a highly distorted,energetically less favorable conformation(for 3).Depending on the solvent for the growth of crystals,compound 3 could also gave rise to a halogen bonded supramolecular double helix.
基金Financial support from the National Natural Science Foundation of China (Nos. 21672227, 21922113, 21988102, 22071257)Chinese Academy of Sciences (Nos. XDB17000000)+2 种基金the National Key Research and Development Program (No. 2017YFA0206903)K. C.Wong Education Foundationthe TIPC Director’s Fund。
文摘Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we report a novel macrocycle WreathArene,a fluorinated C;-symmetrical [1;]-paracyclophane.In the crysalline state,WreathArene features vip-adaptive polymorphism for polyhaloalkanes including chloroform,tribromomethane,1,1,2-trichloroethane,and 1,2-dibromoethane.Non-covalent C-halogen…πinteractions are observed in all of these host-vip structures.Based on these properties,the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.
