Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due ...Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).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
A luminescent and injectable supramolecular hydrogel was successfully constructed through the non- covalent cross-linking of polymers mediated by tetraphenylethylene-bridged cyclodextrin oligomers, presenting the stro...A luminescent and injectable supramolecular hydrogel was successfully constructed through the non- covalent cross-linking of polymers mediated by tetraphenylethylene-bridged cyclodextrin oligomers, presenting the strong blue fluorescence, the reversible gelation behavior responsive to various external stimuli and the good mechanical property of shear thinning.展开更多
Perylene derivative with circularly polarized luminescence(CPL) at aggregated state was seldom reported due to the strong ACQ(aggregation-caused quench) effect at aggregation. In this work, a novel cholesterol-tetraph...Perylene derivative with circularly polarized luminescence(CPL) at aggregated state was seldom reported due to the strong ACQ(aggregation-caused quench) effect at aggregation. In this work, a novel cholesterol-tetraphenylethylene-perylene derivative(TPE-P) was designed and synthesized in moderate yield. It exhibited liquid crystalline behavior with orderly hexagonal columnar mesophase and good fluorescence emission at long wavelength(600-700 nm) not only in solution but also at aggregated states based on the AIE(aggregation-induced emission)-FRET(fluorescence resonance energy transfer) effect between tetraphenylethylene unit and perylene moiety. Moreover, the circular dichroism(CD) and CPL studies suggested the effective chiral transfer from cholesterol unit to tetraphenylethylene unit and perylene skeleton due to the spiral liquid crystalline self-assembly. The CD and CPL signals showed the order of THF < THF-hexane < solid film < meosphase, indicating that the higher spiral orderly degree resulted in the stronger chiral transfer. The largest |glum| value for mesophase excited at 320 nm was as high as 1.5×10^(−2) based on the combining effect of AIE-FRET and chiral transfer. This research not only reported a novel CPL perylene derivative at aggregated state, but also confirmed that the combination of AIE-FRET effect and chiral transfer of liquid crytalline phase was an effective method to construct normal dye with excellent CPL property in aggregated state.展开更多
Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the ba...Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the bad water solubility.In this research,a new cationic amphiphilic TPE-functionalized pyridine salt(TPE-OTs)was designed,which shows good water solubility and hydrochromic properties.The optical properties of the compound have been studied,which is equipped with the typical AIEE characteristics and TICT effect.The compound can self-assemble to form aggregates with a particle size of about 30 nm in water.What is more,the compound is responsive to the environmental humidity,whose fluorescent color changes from green to yellow as the humidity gradually increased.Based on this characteristic,we applied it to the fluorescent anti-counterfeiting ink,realizing the protection and encryption of information.展开更多
We report the preparation and emission properties of tetraphenylethylene(TPE)-based metallacages with aggregation-induced emission(AIE)activities through coordination-driven self-assembly.Two supramolecular cages,[Zn6...We report the preparation and emission properties of tetraphenylethylene(TPE)-based metallacages with aggregation-induced emission(AIE)activities through coordination-driven self-assembly.Two supramolecular cages,[Zn6LA3]and[Zn6LB3],were assembled via TPE-decorated terpyridine(tpy)ligands,LA and LB,respectively,with Zn(II)ions.We performed a subtle change by introducing extra alkyne connectivity into LB to increase the degree of conjugation and geometric constraint,compared with LA.As a result,we obtained a highly emissive cage,[Zn6LB3],even in a dilute solution.展开更多
A water-stable porous anionic metal-organic framework(MOF),[(CH3)2NH2][In(TCPP)4/3]n·(2DMF)n(3H2O)n(1,TCPP=1,1,2,2-tetra(4-carboxylbiphenyl)ethylene),was synthesized.Here,compound 1 showed extremely high sensitiv...A water-stable porous anionic metal-organic framework(MOF),[(CH3)2NH2][In(TCPP)4/3]n·(2DMF)n(3H2O)n(1,TCPP=1,1,2,2-tetra(4-carboxylbiphenyl)ethylene),was synthesized.Here,compound 1 showed extremely high sensitivity and selectivity to current general-purpose pesticide 2,6-dichloro-4-nitroaniline(DCN)in aqueous solution.The fluorescence intensity of compound 1 could be decreased as much as 80%by 6 mL DCN,and it was almost completely quenched only with 20 mL DCN.The results indicate that compound 1 can act as a fluorescent probe for DCN.展开更多
The poly(allylamine hydrochloride)-g-pyrene-tetraphenylethylene(PAH-g-Py-g-TPE)copolymers with different ratios of Py and TPE are synthesized by grafting 1-pyrenecarboxaldehyde(Py-CHO)and tetraphenylethylene-carboxald...The poly(allylamine hydrochloride)-g-pyrene-tetraphenylethylene(PAH-g-Py-g-TPE)copolymers with different ratios of Py and TPE are synthesized by grafting 1-pyrenecarboxaldehyde(Py-CHO)and tetraphenylethylene-carboxaldehyde(TPE-CHO)to PAH via a Schiff base reaction in methanol.The PAH-g-Py-g-TPE forms spherical micelles in water regardless of the ratios of Py and TPE,which can transform into different nanostructures after being incubated in pH 0 and pH 2 solutions,respectively.These nanomaterials including nanoparticles(NPs),nano-rods(NRs),nanotubes(NTs)and nanoribbons(NBs)are composed of Py-CHO and TPE-CHO with different ratios,and emit fluorescence with colors different from the pure Py NRs and NTs,and TPE NPs.展开更多
Isolation of E-1,2-bis(4-bromophenyl)-1,2-diphenyl-ethylene from the E/Z isomer mixture obtained by a Mc Murry coupling reaction and reaction of this isomer with imidazole followed by N-alkylation with n Bu Br and ani...Isolation of E-1,2-bis(4-bromophenyl)-1,2-diphenyl-ethylene from the E/Z isomer mixture obtained by a Mc Murry coupling reaction and reaction of this isomer with imidazole followed by N-alkylation with n Bu Br and anion exchange yielded the bisimidazolium tetraphenylethylene(TPE)derivative H_(2)-E-1(PF_(6))_(2).The reaction of H_(2)-E-1(PF_(6))_(2) with Ag_(2)O yielded the dinuclear metallarectangle[Ag_(2)(E-1)2](PF_(6))_(2) where the two bis-NHC donors E-1 bridge two silver atoms.Irradiation of[Ag_(2)(E-1)2](PF_(6))_(2) leads to E/Z isomerization of the di-NHC ligand and formation of Z-1 in the mononuclear complex[Ag(Z-1)]PF_(6).Demetallation of the di-NHC ligand with NH_(4)Cl/NH_(4)PF_(6) yielded bisimidazolium salt H_(2)-Z-1(PF_(6))_(2).The unique isomerization of the E-TPE derivative into its Z-isomer via metal complex formation/irradiation/demetallation cannot be achieved by irradiation of the individual imidazolium salt.The emissive properties of the TPE complexes[Ag_(2)(E-1)2](PF_(6))_(2) and[Ag(Z-1)]PF_(6) have been investigated.展开更多
Tetraphenylethylene （TPE） based molecules with easy synthesis, good thermal stability, and especially their aggregation-induced emissions enhancement （AIEE） effect recently become attractive organic emitting mater...Tetraphenylethylene （TPE） based molecules with easy synthesis, good thermal stability, and especially their aggregation-induced emissions enhancement （AIEE） effect recently become attractive organic emitting materials due to their potentially practical application in OLEDs. Herein, the AIEE behaviors of tetraphenylethylene dyes （TMTPE and TBTPE） were investigated. Fabricated luminesent device using TMTPE dye as emitting layer displays two strong emitting bands： the blue emission coming from the first-step aggregation and the yellow emission attrib- uted to the second-step aggregation. Thus, it can be utilized to fabricate the white-light OLEDs （WOLEDs） of the single-emitting-component. A three-layer device with the brightness of 1200 cd·m^-2 and current efficiency of 0.78 cd·A^-1 emits the close to white light with the CIE coordinates of x=0.333 and y=0.358, when applied voltage from 8-13 V, verifying that the TPE-based dyes of AIEE effect can be effectively applied in single-emitting- component WOLEDs fabrication.展开更多
The interaction between organic photoelectric molecules leads to the formation of a certain aggregation structure,which plays a pivotal role in the charge transport at the intermolecular interface.In view of this,we i...The interaction between organic photoelectric molecules leads to the formation of a certain aggregation structure,which plays a pivotal role in the charge transport at the intermolecular interface.In view of this,we investigated the mechanism and law of intermolecular interaction by detecting the self-assembled behaviors between organic photoelectric molecules at the interface by scanning tunneling microscopy(STM).In this work,the structural transformations of tetraphenylethylene acids(H_(4)ETTCs)on graphite surface induced by temperature and triazine derivatives(zcy-19,zcy-27,and zcy-38 molecules)were studied by STM technology and density functional theory(DFT)calculations.At room temperature,zcy-19 and H_(4)ETTC molecules formed a small range of ordered co-assembled nanostructure,while for zcy-27 or zcy-38 molecules,no co-assembled nanostructures were observed and only their own self-assembled structures existed on graphite surface,individually.In the thermal annealing trials,the original co-assembled H_(4)ETTC/zcy-19 structure disappeared,and only zcy-19 and H_(4)ETTC self-assembled in separate domains.Nevertheless,new well-ordered H_(4)ETTC/zcy-27 or H_(4)ETTC/zcy-38 co-assembled structures appeared at different annealing temperatures,respectively.Combined with DFT calculations,we further analyzed the mechanism of such structural transformations by triazine derivatives and temperature.Results reveal that triazine derivatives could interact with H_(4)ETTC by N–H···O and O–H···N hydrogen bondings,and whether temperature or zcy series compounds could achieve successful regulation of H_(4)ETTC assembly behavior is closely associated with the conjugated skeleton length of zcy series compounds.展开更多
Monomers with low symmetries can form different topological structures in the preparation of organic two-dimensional(2D)materials.However,it remains challenging to modulate the topologies in practical synthesis.Levera...Monomers with low symmetries can form different topological structures in the preparation of organic two-dimensional(2D)materials.However,it remains challenging to modulate the topologies in practical synthesis.Leveraging theoretical insights into the formation energy of potential structural configurations,we report the topology modulation of a graphdiyne(GDY)derivative constructed from two-fold symmetric tetrakis(4-ethynylphenyl)ethene precursor by changing solvent combinations in a liquid-liquid interfacial system.An aqueous-organic(water-dichloromethane)interface afforded GDY with a kagome topology while a rhombic topology was formed at an organic-organic(hexane-acetonitrile)interface.A comprehensive evaluation of their structures and optoelectronic properties was conducted through various characterization techniques and theoretical computations.Our study provided new insights to modulate the topology of not only GDY but also other framework structures and obtain topologically pure materials in situations where different topologies are possible during practical synthesis.展开更多
Chirality and luminescence are important for both chemistry and biology,which are highly influenced by aggregation.In this work,a pair of metalated tetraphenylethylene(TPE)-based organic cage enantiomers are reported,w...Chirality and luminescence are important for both chemistry and biology,which are highly influenced by aggregation.In this work,a pair of metalated tetraphenylethylene(TPE)-based organic cage enantiomers are reported,which fea-ture a quadrangular prismatic cage structure.These homochiral cages exhibit concentration-dependent chiral behaviors alongside a propensity for thermodynamic aggregation.Aggregation caused quench effect is found for these cages accom-panying the increasing of the concentrations.When a poor solvent is added to produce a kinetical aggregation,the aggregation-annihilation circular dichroism and aggregation-induced emission behaviors are observed for these enantiomeric cages.By comparing these observations with the photophysical behaviors of a pair of structurally similar organic molecular enantiomers,the unique photophysical proper-ties observed are intricately linked to the metal-integrated TPE-functionalized cage structures.展开更多
This study examines the use of an aggregation-induced enhanced emission fluorophore(TPE-MRh)to prepare red-emitting luminescent solar concentrators(LSCs)based on poly(methyl methacrylate)(PMMA)and poly(cyclohexyl meth...This study examines the use of an aggregation-induced enhanced emission fluorophore(TPE-MRh)to prepare red-emitting luminescent solar concentrators(LSCs)based on poly(methyl methacrylate)(PMMA)and poly(cyclohexyl methacrylate)(PCMA).TPE-MRh is a tetraphenylethylene(TPE)derivative bearing two dimethylamino push groups and a 3-methyl-rhodanine pull moiety,with absorption maxima at around 500 nm and fluorescence peak at 700 nm that strongly increases in solid-state.TPE-MRh displays a typical crystallizationinduced enhanced emission that has been rationalized by modeling the compound behavior in solution and solid-state via density functional theory calculations with the inclusion of the environment.TPE-MRh dispersed into 5×5 cm2 polymer films with a thickness of 25±5μm has revealed a partial fluorescence quenching with fluorophore content.Quantum yields(QYs)below 10%for the 2 wt.%of doping have been addressed to the formation of less emissive micro-sized clusters of fluorophores.PMMA slabs with the same surface size but 3 mm of thickness and 200 ppm of TPE-MRh have provided QY of 36.5%thanks to the attenuation of the detrimental effects of fluorophore aggregation.This feature is reflected in the LSCs performance,with devices achieving the largest power collected by the photovoltaic cell.展开更多
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
To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement ...To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement of CPL,they are not combined together to boost CPL.Here,a new tetraphenylethylene(TPE)tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized.Uniquely,synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies.In the presence of octadecylamine,the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute g_(lum)value up to 0.237.Exceptionally,followed by addition of para-phenylenediamine,the g_(lum)value was successively increased to 0.387 due to formation of bigger helical nanofibers.Compared with that of TPE helicate itself,the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed,which was very rare result for CPL-active materials.Surprisingly,the interaction of TPE helicate with xylylenediamine even gave a gel,which was transformed into suspension by shaking.Unexpectedly,the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other.Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large g_(lum)value.展开更多
Two functional tetraphenylethylene derivatives modified by vinylpyridine and vinylnitrobenzene,respectively,were synthesized by Heck coupling reaction.Their optical behaviors were investigated.The results showed they ...Two functional tetraphenylethylene derivatives modified by vinylpyridine and vinylnitrobenzene,respectively,were synthesized by Heck coupling reaction.Their optical behaviors were investigated.The results showed they had AIE activity in solution.The property in solid state displayed that both of them had reversible mechanochromism.Upon grinding,their fluorescence spectra showed around 13–40nm red-shift,and could return to the original state after solvent fuming.We believe that this work will be helpful for the design of stimuli-responsive materials in future.展开更多
Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the peripher...Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.展开更多
Chirality is one of the most important features of the nature.The recognition of enantiomers plays significant roles in the field of life science,pharmaceutical analysis and food chemistry.Among various recognition me...Chirality is one of the most important features of the nature.The recognition of enantiomers plays significant roles in the field of life science,pharmaceutical analysis and food chemistry.Among various recognition methods,fluorescence spectrometry has attracted much attention of researchers thanks to its high sensitivity and easy operation.Compared with traditional fluorescent probes,chiral molecules with aggregation-induced emission(AIE)have drawn increasing interests due to their huge potential in high-efficiency chemo/biosensors and solid emitters.Chiral AIE luminogens(AIEgens)can not only discriminate two enantiomers with excellent enantioselectivity,but also show general applicability for many chiral analytes,such as chiral acids,amino acids,amines,alcohols.In this review,we mainly summarized the recent development of chiral probes with AIE properties,including chiral tetraphenylethylene(TPE)derivatives,α-cyanostilbene derivatives,Schiff base derivatives and other AIEgens.Their synthetic routes,recognition capabilities and possible working mechanisms were well discussed.It is envisioned that the present review can give some significant guidance for design and synthesis of chiral AIEgens with good enantioselectivity and inspire more readers to join the research of chiral AIE.展开更多
Fluorogens with aggregation-induced emission (AIE) characteristics have recently been widely applied for studying biological events, and fluorogens with “smart” properties are especially desirable. Herein, we ration...Fluorogens with aggregation-induced emission (AIE) characteristics have recently been widely applied for studying biological events, and fluorogens with “smart” properties are especially desirable. Herein, we rationally designed and synthesized a biotinylated and reduction-activatable probe (Cys(StBu)-Lys(biotin)-Lys(TPE)-CBT (1)) with AIE properties for cancer-targeted imaging. The biotinylated probe 1 can be actively uptaken by the biotin receptor-overexpressing cancer cells, and then “smartly” self-assemble into nanoparticles inside cells and turn the fluorescence “On”. Employing this “smart” strategy, we successfully applied probe 1 for cancer-targeted imaging. We envision that this biotinylated intelligent probe 1 might be further developed for cancer-targeted imaging in routine clinical studies in the near future.展开更多
基金financially supported by STCSM (No. 16XD 1401000)Program for Changjiang Scholars and Innovative Research Team in University
文摘Tetraphenylethylene(TPE) and its derivatives, as the widely used aggregation-induced emission(AIE) fluorophores, have attracted rapidly growing interest in the fields of material science and biological technology due to their unique light-emitting mechanism—they are nearly non-emissive in dilute solution but emit brilliant fluorescence in the aggregate state because of the restriction of intramolecular motion. Coordination-driven self-assembly, which provides a highly effective method to put the individual chromophores together, is consistent with the AIE mechanism of TPE. During the past few years, some AIE-active metal-organic coordination complexes have been successfully constructed via coordination-driven self-assembly, and their AIE properties and applications have been investigated. In this review, we survey the recent progress on TPE-based metal-organic coordination complexes and their applications in fluorescence sensors, cell imaging, and light-emitting materials. We will introduce them from three different types of structures: metallacycles, metallacages, and metal-organic frameworks(MOFs).
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the National Natural Science Foundation of China (Nos. 21432004,21672113 and 91527301)for financial support
文摘A luminescent and injectable supramolecular hydrogel was successfully constructed through the non- covalent cross-linking of polymers mediated by tetraphenylethylene-bridged cyclodextrin oligomers, presenting the strong blue fluorescence, the reversible gelation behavior responsive to various external stimuli and the good mechanical property of shear thinning.
基金support from the National Natural Science Foundation of China(No.21406036)Fujian Science and Technology Project(No.2019N0010)the National Undergraduate Innovation Program in Fujian Normal University(No.cxxl-2021300)were greatly acknowledged.
文摘Perylene derivative with circularly polarized luminescence(CPL) at aggregated state was seldom reported due to the strong ACQ(aggregation-caused quench) effect at aggregation. In this work, a novel cholesterol-tetraphenylethylene-perylene derivative(TPE-P) was designed and synthesized in moderate yield. It exhibited liquid crystalline behavior with orderly hexagonal columnar mesophase and good fluorescence emission at long wavelength(600-700 nm) not only in solution but also at aggregated states based on the AIE(aggregation-induced emission)-FRET(fluorescence resonance energy transfer) effect between tetraphenylethylene unit and perylene moiety. Moreover, the circular dichroism(CD) and CPL studies suggested the effective chiral transfer from cholesterol unit to tetraphenylethylene unit and perylene skeleton due to the spiral liquid crystalline self-assembly. The CD and CPL signals showed the order of THF < THF-hexane < solid film < meosphase, indicating that the higher spiral orderly degree resulted in the stronger chiral transfer. The largest |glum| value for mesophase excited at 320 nm was as high as 1.5×10^(−2) based on the combining effect of AIE-FRET and chiral transfer. This research not only reported a novel CPL perylene derivative at aggregated state, but also confirmed that the combination of AIE-FRET effect and chiral transfer of liquid crytalline phase was an effective method to construct normal dye with excellent CPL property in aggregated state.
基金financially supported by the National Natural Science Foundation of China(Nos.52173102,21774070 and 21602124)Fluorine Silicone Materials Collaborative Fund of Shandong Provincial Natural Science Foundation(Nos.ZR2021LFG001,ZR2021LFG007)the Young Scholars Program of Shandong University(No.2018WLJH40)。
文摘Since the discovery of aggregation induced emission(AIE)phenomenon,various stimuli-responsive materials have been rapidly developed,but there are still great challenges in the application of ink printing due to the bad water solubility.In this research,a new cationic amphiphilic TPE-functionalized pyridine salt(TPE-OTs)was designed,which shows good water solubility and hydrochromic properties.The optical properties of the compound have been studied,which is equipped with the typical AIEE characteristics and TICT effect.The compound can self-assemble to form aggregates with a particle size of about 30 nm in water.What is more,the compound is responsive to the environmental humidity,whose fluorescent color changes from green to yellow as the humidity gradually increased.Based on this characteristic,we applied it to the fluorescent anti-counterfeiting ink,realizing the protection and encryption of information.
基金support from the National Natural Science Foundation of China(21835001,51773080,and 21674041 for B.X.)the Natural Science Foundation of Jilin Province(20180101297JC for M.W.)the“Talents Cultivation Program”of Jilin University for B.X.
文摘We report the preparation and emission properties of tetraphenylethylene(TPE)-based metallacages with aggregation-induced emission(AIE)activities through coordination-driven self-assembly.Two supramolecular cages,[Zn6LA3]and[Zn6LB3],were assembled via TPE-decorated terpyridine(tpy)ligands,LA and LB,respectively,with Zn(II)ions.We performed a subtle change by introducing extra alkyne connectivity into LB to increase the degree of conjugation and geometric constraint,compared with LA.As a result,we obtained a highly emissive cage,[Zn6LB3],even in a dilute solution.
基金Supported by Supporting Plan for Scientific and Technological Innovative Talents in Universities of Henan Province(No.20HASTIT006)。
文摘A water-stable porous anionic metal-organic framework(MOF),[(CH3)2NH2][In(TCPP)4/3]n·(2DMF)n(3H2O)n(1,TCPP=1,1,2,2-tetra(4-carboxylbiphenyl)ethylene),was synthesized.Here,compound 1 showed extremely high sensitivity and selectivity to current general-purpose pesticide 2,6-dichloro-4-nitroaniline(DCN)in aqueous solution.The fluorescence intensity of compound 1 could be decreased as much as 80%by 6 mL DCN,and it was almost completely quenched only with 20 mL DCN.The results indicate that compound 1 can act as a fluorescent probe for DCN.
基金supported by Ph.D.Programs Foundation of Ministry of Education of China(No.20110101130005)the National Natural Science Foundation of China(No.51120135001).
文摘The poly(allylamine hydrochloride)-g-pyrene-tetraphenylethylene(PAH-g-Py-g-TPE)copolymers with different ratios of Py and TPE are synthesized by grafting 1-pyrenecarboxaldehyde(Py-CHO)and tetraphenylethylene-carboxaldehyde(TPE-CHO)to PAH via a Schiff base reaction in methanol.The PAH-g-Py-g-TPE forms spherical micelles in water regardless of the ratios of Py and TPE,which can transform into different nanostructures after being incubated in pH 0 and pH 2 solutions,respectively.These nanomaterials including nanoparticles(NPs),nano-rods(NRs),nanotubes(NTs)and nanoribbons(NBs)are composed of Py-CHO and TPE-CHO with different ratios,and emit fluorescence with colors different from the pure Py NRs and NTs,and TPE NPs.
基金the National Natural Science Fund for Distinguished Young Scholars of China(22025107)the National Youth Top-notch Talent Support Program of China+2 种基金Key Science and Technology Innovation Team of Shaanxi Province(2019TD-007,2019JLZ-02)The FM&EM International Joint Laboratory of Northwest Universityfinancial support from the DFG(SFB 858,IRTG 2027)。
文摘Isolation of E-1,2-bis(4-bromophenyl)-1,2-diphenyl-ethylene from the E/Z isomer mixture obtained by a Mc Murry coupling reaction and reaction of this isomer with imidazole followed by N-alkylation with n Bu Br and anion exchange yielded the bisimidazolium tetraphenylethylene(TPE)derivative H_(2)-E-1(PF_(6))_(2).The reaction of H_(2)-E-1(PF_(6))_(2) with Ag_(2)O yielded the dinuclear metallarectangle[Ag_(2)(E-1)2](PF_(6))_(2) where the two bis-NHC donors E-1 bridge two silver atoms.Irradiation of[Ag_(2)(E-1)2](PF_(6))_(2) leads to E/Z isomerization of the di-NHC ligand and formation of Z-1 in the mononuclear complex[Ag(Z-1)]PF_(6).Demetallation of the di-NHC ligand with NH_(4)Cl/NH_(4)PF_(6) yielded bisimidazolium salt H_(2)-Z-1(PF_(6))_(2).The unique isomerization of the E-TPE derivative into its Z-isomer via metal complex formation/irradiation/demetallation cannot be achieved by irradiation of the individual imidazolium salt.The emissive properties of the TPE complexes[Ag_(2)(E-1)2](PF_(6))_(2) and[Ag(Z-1)]PF_(6) have been investigated.
基金The authors are grateful to the National Natural Sci- ence Foundation of China （No. 50973077）, the Natural Science Foundation of Jiangsu Province Education Committee （No. 11KJA430003）, Project of Person with Ability of Jiangsu Province （No. 2010-xcl-015） and the Priority Academic Program Development of Jiangsu Higher Education Institutions （PAPD） for financial supports, and Open Project of Jiangsu Key Laboratory for Advanced Optical Manufacture Technologies （No. KJS I 102）.
文摘Tetraphenylethylene （TPE） based molecules with easy synthesis, good thermal stability, and especially their aggregation-induced emissions enhancement （AIEE） effect recently become attractive organic emitting materials due to their potentially practical application in OLEDs. Herein, the AIEE behaviors of tetraphenylethylene dyes （TMTPE and TBTPE） were investigated. Fabricated luminesent device using TMTPE dye as emitting layer displays two strong emitting bands： the blue emission coming from the first-step aggregation and the yellow emission attrib- uted to the second-step aggregation. Thus, it can be utilized to fabricate the white-light OLEDs （WOLEDs） of the single-emitting-component. A three-layer device with the brightness of 1200 cd·m^-2 and current efficiency of 0.78 cd·A^-1 emits the close to white light with the CIE coordinates of x=0.333 and y=0.358, when applied voltage from 8-13 V, verifying that the TPE-based dyes of AIEE effect can be effectively applied in single-emitting- component WOLEDs fabrication.
基金financially supported by the National Natural Science Foundation of China(Nos.22272039 and 21972031)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB36000000)the Jilin Chinese Academy of Sciences-Yanshen Technology Co.,Ltd.
文摘The interaction between organic photoelectric molecules leads to the formation of a certain aggregation structure,which plays a pivotal role in the charge transport at the intermolecular interface.In view of this,we investigated the mechanism and law of intermolecular interaction by detecting the self-assembled behaviors between organic photoelectric molecules at the interface by scanning tunneling microscopy(STM).In this work,the structural transformations of tetraphenylethylene acids(H_(4)ETTCs)on graphite surface induced by temperature and triazine derivatives(zcy-19,zcy-27,and zcy-38 molecules)were studied by STM technology and density functional theory(DFT)calculations.At room temperature,zcy-19 and H_(4)ETTC molecules formed a small range of ordered co-assembled nanostructure,while for zcy-27 or zcy-38 molecules,no co-assembled nanostructures were observed and only their own self-assembled structures existed on graphite surface,individually.In the thermal annealing trials,the original co-assembled H_(4)ETTC/zcy-19 structure disappeared,and only zcy-19 and H_(4)ETTC self-assembled in separate domains.Nevertheless,new well-ordered H_(4)ETTC/zcy-27 or H_(4)ETTC/zcy-38 co-assembled structures appeared at different annealing temperatures,respectively.Combined with DFT calculations,we further analyzed the mechanism of such structural transformations by triazine derivatives and temperature.Results reveal that triazine derivatives could interact with H_(4)ETTC by N–H···O and O–H···N hydrogen bondings,and whether temperature or zcy series compounds could achieve successful regulation of H_(4)ETTC assembly behavior is closely associated with the conjugated skeleton length of zcy series compounds.
基金This research is supported by A*STAR(Nos.C233312013 and 222D800034).
文摘Monomers with low symmetries can form different topological structures in the preparation of organic two-dimensional(2D)materials.However,it remains challenging to modulate the topologies in practical synthesis.Leveraging theoretical insights into the formation energy of potential structural configurations,we report the topology modulation of a graphdiyne(GDY)derivative constructed from two-fold symmetric tetrakis(4-ethynylphenyl)ethene precursor by changing solvent combinations in a liquid-liquid interfacial system.An aqueous-organic(water-dichloromethane)interface afforded GDY with a kagome topology while a rhombic topology was formed at an organic-organic(hexane-acetonitrile)interface.A comprehensive evaluation of their structures and optoelectronic properties was conducted through various characterization techniques and theoretical computations.Our study provided new insights to modulate the topology of not only GDY but also other framework structures and obtain topologically pure materials in situations where different topologies are possible during practical synthesis.
基金National Natural Science Foundation of China,Grant/Award Numbers:22375075,22171106,21731002,21975104,22301103,22201101Guangdong Major Project of Basic and Applied Research,Grant/Award Number:2019B030302009+4 种基金Natural Science Foundation of Guangdong Province,Grant/Award Number:2022A1515011937Fundamental Research Funds for the Central Universities,Grant/Award Number:21622103China Postdoctoral Science Foundation,Grant/Award Numbers:2022M711327,2023T160269Guangdong Provincial Key Laboratory of Speed Capability Research,Grant/Award Number:2023B1212010009Jinan University。
文摘Chirality and luminescence are important for both chemistry and biology,which are highly influenced by aggregation.In this work,a pair of metalated tetraphenylethylene(TPE)-based organic cage enantiomers are reported,which fea-ture a quadrangular prismatic cage structure.These homochiral cages exhibit concentration-dependent chiral behaviors alongside a propensity for thermodynamic aggregation.Aggregation caused quench effect is found for these cages accom-panying the increasing of the concentrations.When a poor solvent is added to produce a kinetical aggregation,the aggregation-annihilation circular dichroism and aggregation-induced emission behaviors are observed for these enantiomeric cages.By comparing these observations with the photophysical behaviors of a pair of structurally similar organic molecular enantiomers,the unique photophysical proper-ties observed are intricately linked to the metal-integrated TPE-functionalized cage structures.
基金MIUR-PRIN,Grant/Award Number:20179BJNA2European Union’s Horizon 2020 Research and Innovation Program,Grant/Award Number:648558China Scholarship Council,Grant/Award Number:202006890004。
文摘This study examines the use of an aggregation-induced enhanced emission fluorophore(TPE-MRh)to prepare red-emitting luminescent solar concentrators(LSCs)based on poly(methyl methacrylate)(PMMA)and poly(cyclohexyl methacrylate)(PCMA).TPE-MRh is a tetraphenylethylene(TPE)derivative bearing two dimethylamino push groups and a 3-methyl-rhodanine pull moiety,with absorption maxima at around 500 nm and fluorescence peak at 700 nm that strongly increases in solid-state.TPE-MRh displays a typical crystallizationinduced enhanced emission that has been rationalized by modeling the compound behavior in solution and solid-state via density functional theory calculations with the inclusion of the environment.TPE-MRh dispersed into 5×5 cm2 polymer films with a thickness of 25±5μm has revealed a partial fluorescence quenching with fluorophore content.Quantum yields(QYs)below 10%for the 2 wt.%of doping have been addressed to the formation of less emissive micro-sized clusters of fluorophores.PMMA slabs with the same surface size but 3 mm of thickness and 200 ppm of TPE-MRh have provided QY of 36.5%thanks to the attenuation of the detrimental effects of fluorophore aggregation.This feature is reflected in the LSCs performance,with devices achieving the largest power collected by the photovoltaic cell.
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National Natural Science Foundation of China(Nos.22072050,22372066 and 22301090)the Open Research Fund(No.2024JYBKF05)of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST)Ministry of Educationthe China Postdoctoral Science Foundation(No.2023M731189)for financial support,and thank the Analytical and Testing Centre at Huazhong University of Science and Technology for measurement.
文摘To get large dissymmetric factor(g_(lum))of organic circularly polarized luminescence(CPL)materials is still a great challenge.Although helical chirality and planar chirality are usual efficient access to enhancement of CPL,they are not combined together to boost CPL.Here,a new tetraphenylethylene(TPE)tetracycle acid helicate bearing both helical chirality and planar chirality was designed and synthesized.Uniquely,synergy of the helical chirality and planar chirality was used to boost CPL signals both in solution and in helical self-assemblies.In the presence of octadecylamine,the TPE helicate could form helical nanofibers that emitted strong CPL signals with an absolute g_(lum)value up to 0.237.Exceptionally,followed by addition of para-phenylenediamine,the g_(lum)value was successively increased to 0.387 due to formation of bigger helical nanofibers.Compared with that of TPE helicate itself,the CPL signal of the self-assemblies was not only magnified by 104-fold but also inversed,which was very rare result for CPL-active materials.Surprisingly,the interaction of TPE helicate with xylylenediamine even gave a gel,which was transformed into suspension by shaking.Unexpectedly,the suspension showed 40-fold stronger CPL signals than the gel with signal direction inversion each other.Using synergy of the helical chirality and planar chirality to significantly boost CPL intensity provides a new strategy in preparation of organic CPL materials having very large g_(lum)value.
基金financially supported by the National Natural Science Foundation of China(Nos.21676113,21402057,21772054)Distinguished Young Scholar of Hubei Province(No.2018CFA079)+5 种基金Youth Chen-Guang Project of Wuhan(No.2016070204010098)the 111 Project(No.B17019)the Ministry-Province Jointly Constructed Base for State Key Lab-Shenzhen Key Laboratory of Chemical Biology(Shenzhen),the State Key Laboratory of Materials-Oriented Chemical Engineering(No.KL17-10)the Open Project Fund of Key Laboratory of Natural Resources of Changbai Mountain&Functional Molecules,Yanbian University,Ministry of Education(No.NRFM201701)the Foundation of Key Laboratory of Synthetic and Biological Colloids,Jiangnan University,Ministry of Education(No.JDSJ2017-07)Self-determined Research Funds of CCNU from the Colleges’Basic Research and Operation of MOE(No.CCNU18TS012)
文摘Two functional tetraphenylethylene derivatives modified by vinylpyridine and vinylnitrobenzene,respectively,were synthesized by Heck coupling reaction.Their optical behaviors were investigated.The results showed they had AIE activity in solution.The property in solid state displayed that both of them had reversible mechanochromism.Upon grinding,their fluorescence spectra showed around 13–40nm red-shift,and could return to the original state after solvent fuming.We believe that this work will be helpful for the design of stimuli-responsive materials in future.
基金the National Natural Science Foundation of China(Nos.21274016 and 21072026)Fundamental Research Funds for the Central Universities(No.DUT13LK06)for financial support to this work
文摘Two novel thieno-[3,4-b]-pyrazine-based molecules, TP-E and TP-O, were designed and synthesized for potential application as red fluorescent emitters. The bulky tetraphenylethylene groups were attached at the periphery of the thieno-[3,4-b]-pyrazine core to form the non-planar molecules, as efficient solid- state emitting materials. The peripheral groups were grafted to the emissive core through either a conjugated acetylene bond, or a non-conjugated ether bond. These molecules exhibit strnng red fluorescence in both dilute solutions and in thin films with large Stokes shifts of over 100 nm. The cyclic voltammetry measurements showed the reversible oxidation and reduction behavior for both compounds. All these properties indicate the two compounds are possible functional materials for use in ontoelectronic devices.
基金partially supported by the National Natural Science Foundation of China(Nos.52173152,21805002)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110476)+2 种基金the Fund of the Rising Stars of Shaanxi Province(No.2021KJXX-48)Scientific and Technological Innovation Team of Shaanxi Province(No.2022TD-36)Scientific Research Program Funded by Shaanxi Provincial Education Department(No.22JK0247)。
文摘Chirality is one of the most important features of the nature.The recognition of enantiomers plays significant roles in the field of life science,pharmaceutical analysis and food chemistry.Among various recognition methods,fluorescence spectrometry has attracted much attention of researchers thanks to its high sensitivity and easy operation.Compared with traditional fluorescent probes,chiral molecules with aggregation-induced emission(AIE)have drawn increasing interests due to their huge potential in high-efficiency chemo/biosensors and solid emitters.Chiral AIE luminogens(AIEgens)can not only discriminate two enantiomers with excellent enantioselectivity,but also show general applicability for many chiral analytes,such as chiral acids,amino acids,amines,alcohols.In this review,we mainly summarized the recent development of chiral probes with AIE properties,including chiral tetraphenylethylene(TPE)derivatives,α-cyanostilbene derivatives,Schiff base derivatives and other AIEgens.Their synthetic routes,recognition capabilities and possible working mechanisms were well discussed.It is envisioned that the present review can give some significant guidance for design and synthesis of chiral AIEgens with good enantioselectivity and inspire more readers to join the research of chiral AIE.
基金supported by Anhui Scientific and Technological Project(No.1704a0802164)the Natural Science Foundation of the Anhui Higher Education Institutions of China(No.KJ2018A0192)
文摘Fluorogens with aggregation-induced emission (AIE) characteristics have recently been widely applied for studying biological events, and fluorogens with “smart” properties are especially desirable. Herein, we rationally designed and synthesized a biotinylated and reduction-activatable probe (Cys(StBu)-Lys(biotin)-Lys(TPE)-CBT (1)) with AIE properties for cancer-targeted imaging. The biotinylated probe 1 can be actively uptaken by the biotin receptor-overexpressing cancer cells, and then “smartly” self-assemble into nanoparticles inside cells and turn the fluorescence “On”. Employing this “smart” strategy, we successfully applied probe 1 for cancer-targeted imaging. We envision that this biotinylated intelligent probe 1 might be further developed for cancer-targeted imaging in routine clinical studies in the near future.
