Supramolecular self-assembly,an important strategy in nanotechnology,has been widely studied in the past two decades.In this review,we have introduced the recent progress on construction of two-dimensional(2D)nanostru...Supramolecular self-assembly,an important strategy in nanotechnology,has been widely studied in the past two decades.In this review,we have introduced the recent progress on construction of two-dimensional(2D)nanostructures by host-guest supramolecular chemistry at solid-liquid interface,and the interactions between the host assembly and the guest molecules are the major concerns.At first,the hydrogen bonds connected hybrid structures are discussed.And then we have paid a close attention on the surface-confined condensation reactions that has flourished recently in direct preparing novel nanostructures with increasing structural complexity.In the end,the cavity confinement of the 2D supramolecular host-guest architectures has been studied.On the basis of the above-mentioned interactions,a group of functional hybrid structures have been prepared.Notably,scanning tunneling microscopy(STM),a unique technique to probe the surface morphology and information at the single molecule level,has been used to probe the formed structures on highly oriented pyrolytic graphite(HOPG)surface.展开更多
Metal-free room-temperature phosphorescence(RTP)materials have the characteristics of large Stokes shift,long lifetime,and triplet state transition.They exhibit application potential in various fields,such as bioimagi...Metal-free room-temperature phosphorescence(RTP)materials have the characteristics of large Stokes shift,long lifetime,and triplet state transition.They exhibit application potential in various fields,such as bioimaging,computer display,sensor,and anticounterfeiting and have drawn much research interest.Recent work showed that manipulating intermolecular interactions(e.g.,crystallization,polymerization,and rigid matrix)and host-guest assembly to restrain nonradiative transitions and isolate phosphor from oxygen as much as possible is a feasible way to obtain various types of efficient RTP materials.In some cases,intermolecular interactions also facilitated RTP emission by regulating the triplet state.On the other hand,heavy atoms(Br,I,etc.),heteroatoms(N,O,S,etc.),or carbonyls were introduced to the molecular skeleton through molecular engineering to enhance intersystem crossing,which is important for populating the triplet exciton.By comprehensively using the aforesaid strategies,great progress has been made for RTP materials.In this mini-review,we summarized recent advances in organic RTP materials based on manipulating intermolecular interactions.Typical host-guest assembly,hydrogen-bond assembly,energy transfer process,and exciplex emission system-based RTP materials were well illustrated.In summary,the current challenges and prospects for development in this field were presented.展开更多
The field of supramolecular chemistry is rapidly progressing,transitioning from the creation of thermodynamically stable systems found in local or global minima on the free energy landscape to the development of out-o...The field of supramolecular chemistry is rapidly progressing,transitioning from the creation of thermodynamically stable systems found in local or global minima on the free energy landscape to the development of out-of-equilibrium systems that rely on chemical reactions to establish and maintain their structures.Over the past decade,numerous artificial out-of-equilibrium systems have been devised in various domains of supramolecular chemistry,many of which have been extensively reviewed.However,one area that has received limited attention thus far is the use of out-of-equilibrium processes to regulate host-guest interactions.This minireview aims to address this gap by exploring the construction of out-ofequilibrium systems based on host-guest complexation,which likely employs similar strategies to those employed in analogous noncovalent interactions.The review begins with a summary of these shared strategies.Subsequently,it discusses representative publications that exemplify these strategies and classifies thembased onwhich component is being modulated-host,guest,or competitive molecules.Through this examination,our objective is to shed light on the design of out-of-equilibrium systems relying on host-guest interactions and provide valuable insights into the preparation strategies for various transient materials.展开更多
The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the guest molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy...The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the guest molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy(STM).STM observations display that two kinds of nanostructures are fabricated by H3 BDA molecules through intermolecular hydrogen bonds,in which a linear structure is formed at a higher con-centration and a flower-like structure is obtained at a lower concentration.After the addition of COR and T4PT,H_(3) BDA appears different responsiveness resulting in different co-assembled structures,respectively.The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities.When the pyridine derivative(T4PT)is introduced,a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine.Furthermore,the deposition of additional COR to the H_(3) BDA/T4PT system results in the breakdown of the porous structure and the generation of H_(3) BDA/COR host-guest system.Combined with density functional theory(DFT)calculations and molecular dynamics(MD)simulations,the transformation phenomenon of bi-component nanostruc-ture induced by guest molecules is formulated.The results are expected to understand the modification effect of guest molecules on the host network,which is of great significance for the design and construc-tion of multi-component nanostructures and crystal engineering.展开更多
The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-ass...The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-guest assembly.展开更多
Controlling friction by the electric field is a promising way to improve the tribological performance of a variety of movable mechanical systems.In this work,the assembly structure and microscale superlubricity of a h...Controlling friction by the electric field is a promising way to improve the tribological performance of a variety of movable mechanical systems.In this work,the assembly structure and microscale superlubricity of a host–guest assembly are effectively controlled by the electric field.With the help of the scanning tunneling microscopy(STM)technique,the host–guest assembly structures constructed by the co-assembly of fullerene derivative(Fluorene-C60)with macrocycles(4B2A and 3B2A)are explicitly characterized.Combined with density functional theory(DFT),the distinct different assembly behaviors of fullerene derivatives are revealed at different probe biases,which is attributed to the molecular polarity of the fullerene derivative.Through the control on the adsorption behavior,the friction coefficient of host–guest assembly is demonstrated to be controllable in the electric field by using atomic force microscopy(AFM).At positive probe bias,the friction coefficient of the host–guest assembly is significantly reduced and achieves superlubricity(μmin=0.0049).The efforts not only help us gain insight into the host–guest assembly mechanism controlled by the electric field,but also promote the further application of fullerene in micro-electro-mechanical systems(MEMS).展开更多
Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids...Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.展开更多
Inspired by the intriguing capability of beetles to quickly slide on water,scientists have long imagined the use of this surface-tension-gradient-dominated Marangoni motion in various applications,for exam-ple,self-pr...Inspired by the intriguing capability of beetles to quickly slide on water,scientists have long imagined the use of this surface-tension-gradient-dominated Marangoni motion in various applications,for exam-ple,self-propulsion.展开更多
Polyoxometalates(POMs)have drawn broad and intense interest due to their unique structure-dependent prop-erties.The assembly of POM molecules into nanoarchitectures and superstructures can bridge the gap between micro...Polyoxometalates(POMs)have drawn broad and intense interest due to their unique structure-dependent prop-erties.The assembly of POM molecules into nanoarchitectures and superstructures can bridge the gap between micro-molecule and bulk POM materials and integrate the merits of molecule and materials that are widely used in catalysis,energy conversion,electronics,and bioapplications.The synthetic methodologies and applications of multiscale POM assemblies have been widely studied.In this review,we survey the POM-based multiscale assembly focusing on two aspects:the strategies for multiscale assembly of POMs and the emerging applications of POM assemblies.For the multiscale assembly,we focus on the methods of POMs assembly including templated synthesis and self-and co-assembly of POMs into nanoarchitectures and superstructures.For the applications,we review the applications of POM assemblies in energy,catalysis,and functional materials.Finally,we present the prospects for the future synthetic design and applications of POM assemblies.展开更多
Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-m...Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-methyl- imidazolium-3-yl）propane-l-sulfonate, demonstrating both cation binding of imidazolium moiety and anion binding of sulfonate moiety for the first time. Incorporation of dimeric boric acid facilitates the formation of metal-free three-dimensional framework.展开更多
A series of newπ-conjugated macrocycles(AzoM-n-E,n 1–3)incorporating=azobenzene units have been synthesized by a facile strategy in one-pot reaction.The resultant azobenzene-embedded macrocycles feature intrinsic ph...A series of newπ-conjugated macrocycles(AzoM-n-E,n 1–3)incorporating=azobenzene units have been synthesized by a facile strategy in one-pot reaction.The resultant azobenzene-embedded macrocycles feature intrinsic photoresponsive behaviors and intriguing supramolecular assembling properties.The smallest macro-cycle AzoM-1-E with a rigid planar conjugated backbone structure is used to prepare the single crystal transistors,showing reversible optical tunability.The moderate size macrocycle AzoM-2-E assembles into a dimer in the form of interpenetration throughπ-πstacking between azobenzene units.The largest macrocycle AzoM-3-E with enhancedflexibility can adaptively assemble with various types of electron-deficient guests accompanied by distortion of azobenzene.Typically,AzoM-3-E assembles with the planar F4-TCNQ to form a tetragonal geometry by C-F⋅⋅⋅π and π-π interactions,while the assembly with ellipsoidal C70 viaπ-πinteractions induces AzoM-3-E to form a boat-shaped geometry.This work will shed new light on the development of functional conjugated macrocycles in organic electronics.展开更多
The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration...The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-guest complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and guest type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.展开更多
α-Cyanostilbene(CS)based organic luminescent materials with eficient electrical conductivity,aggregation-induced enhanced emission,and controllable multi-colour emission properties,have been aroused wide attention by...α-Cyanostilbene(CS)based organic luminescent materials with eficient electrical conductivity,aggregation-induced enhanced emission,and controllable multi-colour emission properties,have been aroused wide attention by scientists over the past few years.Self-assembly of cS-motif in aqueous me-dia refers to an environment-friendly method for preparing luminescent materials.However,it is still challenging to control the intrinsic hydrophobic properties of the organic components in aqueous media.In this study,an amphiphilic dicyanostilbene-functionalized thiophene(ACSTP)derivative was synthe-sized.Z-AcSTP was identified to dissolve in different organic solvents,accompanied with strong and tun-able fluorescence emission.However,when Z-AcSTP was dispersed in water,it was self-assembled into nanofibers,and the fluorescence was red shifted,accompanied with sharp decrease of intensity com-pared with that in DMSO.Furthermore,Z-form of ACSTP to its E-form under 365 nm irradiation led to the morphology transformation from nanofibers to nanosheets.Notably,upon addition of water-soluble pillar[5]arene(wP5),the nanofibers were transformed into fluorescent hollow particles due to the host-guest interactions between the pyridinium group and WP5 and the obtained fluorescent particles can be further applied in living cell imaging.展开更多
基金supports from the National Basic Research Program of China(2011CB932303,2013CB934200)the National Natural Science Foundation of China(21073048,51173031,91127043)are also gratefully acknowledged
文摘Supramolecular self-assembly,an important strategy in nanotechnology,has been widely studied in the past two decades.In this review,we have introduced the recent progress on construction of two-dimensional(2D)nanostructures by host-guest supramolecular chemistry at solid-liquid interface,and the interactions between the host assembly and the guest molecules are the major concerns.At first,the hydrogen bonds connected hybrid structures are discussed.And then we have paid a close attention on the surface-confined condensation reactions that has flourished recently in direct preparing novel nanostructures with increasing structural complexity.In the end,the cavity confinement of the 2D supramolecular host-guest architectures has been studied.On the basis of the above-mentioned interactions,a group of functional hybrid structures have been prepared.Notably,scanning tunneling microscopy(STM),a unique technique to probe the surface morphology and information at the single molecule level,has been used to probe the formed structures on highly oriented pyrolytic graphite(HOPG)surface.
基金supported by the National Natural Science Foundation of China(21788102,22125803,22020102006,21871083)Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)+3 种基金the Program of Shanghai Academic/Technology Research Leader(20XD1421300)the“Shu Guang”Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(19SG26)the Fundamental Research Funds for the Central Universitiesthe China National Postdoctoral Program for Innovative Talents(BX20220106)。
文摘Metal-free room-temperature phosphorescence(RTP)materials have the characteristics of large Stokes shift,long lifetime,and triplet state transition.They exhibit application potential in various fields,such as bioimaging,computer display,sensor,and anticounterfeiting and have drawn much research interest.Recent work showed that manipulating intermolecular interactions(e.g.,crystallization,polymerization,and rigid matrix)and host-guest assembly to restrain nonradiative transitions and isolate phosphor from oxygen as much as possible is a feasible way to obtain various types of efficient RTP materials.In some cases,intermolecular interactions also facilitated RTP emission by regulating the triplet state.On the other hand,heavy atoms(Br,I,etc.),heteroatoms(N,O,S,etc.),or carbonyls were introduced to the molecular skeleton through molecular engineering to enhance intersystem crossing,which is important for populating the triplet exciton.By comprehensively using the aforesaid strategies,great progress has been made for RTP materials.In this mini-review,we summarized recent advances in organic RTP materials based on manipulating intermolecular interactions.Typical host-guest assembly,hydrogen-bond assembly,energy transfer process,and exciplex emission system-based RTP materials were well illustrated.In summary,the current challenges and prospects for development in this field were presented.
基金the financial support of the Chinese Scholarship Council(CSC)the Science and Technology Department of Shandong Province(grant no.ZR202211300055).
文摘The field of supramolecular chemistry is rapidly progressing,transitioning from the creation of thermodynamically stable systems found in local or global minima on the free energy landscape to the development of out-of-equilibrium systems that rely on chemical reactions to establish and maintain their structures.Over the past decade,numerous artificial out-of-equilibrium systems have been devised in various domains of supramolecular chemistry,many of which have been extensively reviewed.However,one area that has received limited attention thus far is the use of out-of-equilibrium processes to regulate host-guest interactions.This minireview aims to address this gap by exploring the construction of out-ofequilibrium systems based on host-guest complexation,which likely employs similar strategies to those employed in analogous noncovalent interactions.The review begins with a summary of these shared strategies.Subsequently,it discusses representative publications that exemplify these strategies and classifies thembased onwhich component is being modulated-host,guest,or competitive molecules.Through this examination,our objective is to shed light on the design of out-of-equilibrium systems relying on host-guest interactions and provide valuable insights into the preparation strategies for various transient materials.
基金support from the National Natural Science Foundation of China(No.22172055)the Natural Science Foundation of Guangdong Province(Nos.2023B1515040026,2022A1515011892)the Basic and Applied Basic Research Program of Guangzhou City(Nos.202002030083,202102080443)is gratefully acknowledged.
文摘The self-assembled structures of H_(3) BDA molecule with multiple meta-dicarboxylic groups and their stim-ulus responses to the guest molecules(COR and T4PT)are thoroughly investigated by scanning tunneling microscopy(STM).STM observations display that two kinds of nanostructures are fabricated by H3 BDA molecules through intermolecular hydrogen bonds,in which a linear structure is formed at a higher con-centration and a flower-like structure is obtained at a lower concentration.After the addition of COR and T4PT,H_(3) BDA appears different responsiveness resulting in different co-assembled structures,respectively.The linear structure is regulated into a flower-like structure by COR and COR molecules are trapped in the cavities.When the pyridine derivative(T4PT)is introduced,a new bicomponent porous structure emerges via the hydrogen bond formed between the carboxyl group and the pyridine.Furthermore,the deposition of additional COR to the H_(3) BDA/T4PT system results in the breakdown of the porous structure and the generation of H_(3) BDA/COR host-guest system.Combined with density functional theory(DFT)calculations and molecular dynamics(MD)simulations,the transformation phenomenon of bi-component nanostruc-ture induced by guest molecules is formulated.The results are expected to understand the modification effect of guest molecules on the host network,which is of great significance for the design and construc-tion of multi-component nanostructures and crystal engineering.
基金supported by the NSFC(Nos.22065031,22061039,22001214,22165027)the Fundamental Research Funds for the Central Universities(No.31920230145)+4 种基金the Top-Notch Talent Project in Gansu Province,the Key R&D Program of Gansu Province(No.21YF5GA066)Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020-0405-JCC-630,20JR10RA088,21JR1RA220)Gansu Province Science Foundation for Youths(23JRRA690)Northwest Normal University Young Scholars Research Capacity Improvement Program(NWNU-LKQN2023-05).
文摘The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-guest assembly.
基金This work was financially supported by the National Basic Research Program of China(No.2017YFA0205000)the National Natural Science Foundation of China(Nos.51875303 and 21972031)the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000).
文摘Controlling friction by the electric field is a promising way to improve the tribological performance of a variety of movable mechanical systems.In this work,the assembly structure and microscale superlubricity of a host–guest assembly are effectively controlled by the electric field.With the help of the scanning tunneling microscopy(STM)technique,the host–guest assembly structures constructed by the co-assembly of fullerene derivative(Fluorene-C60)with macrocycles(4B2A and 3B2A)are explicitly characterized.Combined with density functional theory(DFT),the distinct different assembly behaviors of fullerene derivatives are revealed at different probe biases,which is attributed to the molecular polarity of the fullerene derivative.Through the control on the adsorption behavior,the friction coefficient of host–guest assembly is demonstrated to be controllable in the electric field by using atomic force microscopy(AFM).At positive probe bias,the friction coefficient of the host–guest assembly is significantly reduced and achieves superlubricity(μmin=0.0049).The efforts not only help us gain insight into the host–guest assembly mechanism controlled by the electric field,but also promote the further application of fullerene in micro-electro-mechanical systems(MEMS).
基金supported by the National Basic Research Program of China (No. 2016YFA0200700)the National Natural Science Foundation of China (Nos. 21773041 and 21472029)
文摘Aromatic carboxylic acid self-assembly has been a hot research field for many scientists due to its strong coordination ability and flexible coordination mode.The hydrogen bond formed between aromatic carboxylic acids is a strong intermolecular force and has directionality and saturation,which plays a very important role in the self-assembly and regulation of aromatic carboxylic acids.In this review,we introduce surface organization formed by aromatic carboxylic acids with the aid of scanning tunneling microscopy(STM).These two-dimensional structures include molecular templates,host-guest systems,and photo-isomerization structures.We also emphasize the thermodynamics and dynamics,which are important research topics of current and future study.
基金This work was supported by the National Natural Science Foundation of China(21674009 and 21604002)Open Project of State Key Laboratory of Supramolecular Structure and Materials(sklssm201816).
文摘Inspired by the intriguing capability of beetles to quickly slide on water,scientists have long imagined the use of this surface-tension-gradient-dominated Marangoni motion in various applications,for exam-ple,self-propulsion.
基金the financial support from the National Natural Science Foundation of China(92161124,52002165)Shenzhen Basic Research Project(JCYJ20210324104808022)+1 种基金Beijing National Laboratory for Molecular Sciences(BNLMS202013)Guangdong Provin-cial Key Laboratory of Catalysis(2020B121201002),and a start-up fund from SUSTech.
文摘Polyoxometalates(POMs)have drawn broad and intense interest due to their unique structure-dependent prop-erties.The assembly of POM molecules into nanoarchitectures and superstructures can bridge the gap between micro-molecule and bulk POM materials and integrate the merits of molecule and materials that are widely used in catalysis,energy conversion,electronics,and bioapplications.The synthetic methodologies and applications of multiscale POM assemblies have been widely studied.In this review,we survey the POM-based multiscale assembly focusing on two aspects:the strategies for multiscale assembly of POMs and the emerging applications of POM assemblies.For the multiscale assembly,we focus on the methods of POMs assembly including templated synthesis and self-and co-assembly of POMs into nanoarchitectures and superstructures.For the applications,we review the applications of POM assemblies in energy,catalysis,and functional materials.Finally,we present the prospects for the future synthetic design and applications of POM assemblies.
基金Project supported by the Science and Technology Fund of Guizhou Province(No.2016-1030)the Innovation Program for High-Level Talents of Guizhou Province(No.2016-5657)the Major Program for Creative Research Groups of Guizhou Provincial Education Department(No.2017-028)~~
文摘Three-component framework of cucurbit[6]uril, 3-（1-methylimidazolium-3-yl）propane-l-sulfonate and boric acid has been constructed. The crystal structure reveals 1 ： 2 host-guest motif of cucurbit[6]uril and 3-（1-methyl- imidazolium-3-yl）propane-l-sulfonate, demonstrating both cation binding of imidazolium moiety and anion binding of sulfonate moiety for the first time. Incorporation of dimeric boric acid facilitates the formation of metal-free three-dimensional framework.
基金National Key R&D Program of China,Grant/Award Number:2018YFA0703200National Natural Science Foundation of China,Grant/Award Numbers:61890940,52073063+1 种基金Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher LearningNatural Science Foundation of Shanghai,Grant/Award Numbers:22ZR1405800,23ZR1405100。
文摘A series of newπ-conjugated macrocycles(AzoM-n-E,n 1–3)incorporating=azobenzene units have been synthesized by a facile strategy in one-pot reaction.The resultant azobenzene-embedded macrocycles feature intrinsic photoresponsive behaviors and intriguing supramolecular assembling properties.The smallest macro-cycle AzoM-1-E with a rigid planar conjugated backbone structure is used to prepare the single crystal transistors,showing reversible optical tunability.The moderate size macrocycle AzoM-2-E assembles into a dimer in the form of interpenetration throughπ-πstacking between azobenzene units.The largest macrocycle AzoM-3-E with enhancedflexibility can adaptively assemble with various types of electron-deficient guests accompanied by distortion of azobenzene.Typically,AzoM-3-E assembles with the planar F4-TCNQ to form a tetragonal geometry by C-F⋅⋅⋅π and π-π interactions,while the assembly with ellipsoidal C70 viaπ-πinteractions induces AzoM-3-E to form a boat-shaped geometry.This work will shed new light on the development of functional conjugated macrocycles in organic electronics.
基金supported by the Innovation Program for Highlevel Talents of Guizhou Province (No. 2016-5657)the University of Hull for support。
文摘The binding interactions between 4-aminopyridine(4-AP) and a series of cucurbit[n]urils(Q[5], Q[6],TMe Q[6], Q[7], Q[8]) have been studied using1H NMR spectroscopy, UV–vis absorption spectroscopy,isothermal titration calorimetry(ITC) and X-ray crystallography. The data indicates that the Q[5]@4-AP complex exhibits exo binding, which is not observed in the other four host-guest complexes. Furthermore,X-ray crystallography clearly reveals how the Q[n]s bind with 4-AP to form complexes, for example Q[5]forms an outer-surface complex, whilst Q[6], TMe Q[6] and Q[7] formed 1:1 host and guest type complexes, and Q[8] formed a stable 1:2 ternary complex due to its large cavity, which can accommodate two 4-AP molecules.
基金supported by the National Natural Science Foundation of China(Nos.21801139,32101215,22007052)Natural Science Foundation of Jiangsu Province(Nos.BK20180942,BK20190917)。
文摘α-Cyanostilbene(CS)based organic luminescent materials with eficient electrical conductivity,aggregation-induced enhanced emission,and controllable multi-colour emission properties,have been aroused wide attention by scientists over the past few years.Self-assembly of cS-motif in aqueous me-dia refers to an environment-friendly method for preparing luminescent materials.However,it is still challenging to control the intrinsic hydrophobic properties of the organic components in aqueous media.In this study,an amphiphilic dicyanostilbene-functionalized thiophene(ACSTP)derivative was synthe-sized.Z-AcSTP was identified to dissolve in different organic solvents,accompanied with strong and tun-able fluorescence emission.However,when Z-AcSTP was dispersed in water,it was self-assembled into nanofibers,and the fluorescence was red shifted,accompanied with sharp decrease of intensity com-pared with that in DMSO.Furthermore,Z-form of ACSTP to its E-form under 365 nm irradiation led to the morphology transformation from nanofibers to nanosheets.Notably,upon addition of water-soluble pillar[5]arene(wP5),the nanofibers were transformed into fluorescent hollow particles due to the host-guest interactions between the pyridinium group and WP5 and the obtained fluorescent particles can be further applied in living cell imaging.
