Metal-organic frameworks(MOFs)containing face-to-faceπ-πinteracting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible[4+...Metal-organic frameworks(MOFs)containing face-to-faceπ-πinteracting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible[4+4]photocycloaddition reaction,but it is extremely challenging to obtain such materials.Herein,we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature.Compounds Dy_(2)(ampH)_(2x)(amp2H_(2))_(3-x)(H_(2)O)_(6)·4H_(2)O[x=0.01,Dy-70;x=0.02,Dy-80;x=0.037,Dy-90;amp_(2)H_(4)=pre-photodimerized 9-anthracenemethylphosphonic acid(amp H_(2))]were obtained by the reaction of DyCl_(3)and amp_(2)H_(4)in water at 70,80,and 90℃,respectively.They all show excimer emission of paired anthracenes at ca.555 nm.Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination,accompanied by luminescence changes.This property further enables Dy-90 to be used for optical anti-counterfeiting.展开更多
Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an imp...Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.展开更多
Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoor...Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoordinate arylboron com-pounds emerge as prominent molecular systems,owing to their captivating photochemical mechanisms and photophysical transformations.In recent years,these molecules have experienced notable progress,leading to the emergence of numerous organic boron photoresponsive molecular systems with innovative structures and exceptional performance.In this comprehensive review,we present a thorough examination of the latest advancements in the field,systematically elucidating the design strategies and structure-activity relationships of these mol-ecules.Furthermore,we delve into the photoresponse mechanisms of various molecules and summarize their unique characteristics.Ultimately,we analyze the challenges,opportunities,and prospects encountered in this exciting field of research.展开更多
Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves c...Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of(Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism(CD), ultraviolet-visible(UV-Vis), fluorescence, ~1 H nuclear magnetic resonance(~1 H-NMR), attenuated total internal reflection Fourier transform Infrared(ATR-FTIR) spectroscopy, and scanning electron microscopy(SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B(SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.展开更多
For the main purpose of manipulating the functions of molecules, researchers have made great achievements on photoresponsive molecules using light as a trigger. Light has become a promising scientific tool due to it b...For the main purpose of manipulating the functions of molecules, researchers have made great achievements on photoresponsive molecules using light as a trigger. Light has become a promising scientific tool due to it being a clean and noninvasive external stimulant. By attachment of photoresponsive moieties to molecules, the biological activities of molecules can be attenuated by light activation. With wide applications of laser in life sciences, it will be possible to achieve high spatiotemporal resolution. In this review, we focus on photoresponsive nucleic acids for photomodulating gene expression with light activation. With incorporation of photoswitchable or photocleavable moieties, biological behaviors of nucleic acids are photoregulated reversibly or irreversibly. Recent development and applications of photoresponsive nucleic acid in vitro and in vivo have shown a very promising future for manipulation of specific functional genes or disease genes. We expect that photoresponsive nucleic acids will be powerful scientific tools for studying biological events as well as gene therapy agents for genetic diseases.展开更多
The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeit...The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeiting. However, to achieve both excellent photoresponsive performance and bright luminescence in solid state remains challenge. Herein, we integrate a novel photochromic fluorophore YL into flexible polymer chains, thereby enabling the resultant polymer PYL with reversible photoisomerization upon aggregation. Remarkably, the polymer PYL possesses excellent photochromic properties and aggregationinduced emission(AIE) activity, which can be attributed to the photoactive YL moiety. Upon light exposure, its film exhibits reversibly off-to-on fluorescent modulation with quick response, high emission efficiency and signal contrast, sharply different from the weak emission in solution. The novel photoresponsive AIE polymer with invisible/visible color and fluorescence transformation allows for advanced anti-counterfeiting applications. This work provides an efficient platform for constructing solid-state photocontrollable luminescent materials.展开更多
A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solub...A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solubility in comparison with their azobenzene analogues. 1.2 to 2-fold activity difference was observed for these azopyridine-imidacloprids against house fly （Musca domestica） and cowpea aphid （Aphis craccivora） upon irradiation.展开更多
In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corres...In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.展开更多
Several kinds of novel azobenzene-containing polyelectrolytes with special molecular design have been developed from acryloyl chloride or epoxy based precursor polymers. The acryloyl chloride based precursor polymer, ...Several kinds of novel azobenzene-containing polyelectrolytes with special molecular design have been developed from acryloyl chloride or epoxy based precursor polymers. The acryloyl chloride based precursor polymer, poly(acryloyl chloride), was prepared by free radical polymerization of acryloyl chloride. The azo polyelectrolytes were prepared by an esterification reaction between the precursor polymer and corresponding azo chromophores containing a reactive hydroxyl group, followed by hydrolysis of the unreacted acyl chloride groups. The epoxy based precursor polymer was prepared by the reaction between 1,4-cyclohexanedimethanol diglycidyl ether and aniline, and postfunctionalized by azo coupling reaction to form azo polymers containing chromophores with ionizable groups. The polyelectrolytes were characterized by elemental analysis, H-1-NMR, IR and UV-Vis spectroscopy. The photodynamic and photoresponsive properties, as well as self-assembly of these azo polyelectrolytes are reported in this paper([1]).展开更多
Smart functional microgels hold great potential in a variety of applications,especially in drug transportation.However,current drug carriers based on physiological internal stimuli cannot efficiently orientate to desi...Smart functional microgels hold great potential in a variety of applications,especially in drug transportation.However,current drug carriers based on physiological internal stimuli cannot efficiently orientate to designated locations.Therefore,it is necessary to introduce the self-propelled particles to the drug release of the microgels.In order to study self-propulsion of microgels induced by light,it is also a challenge to prepare micronsized microgels so that they can be observed directly under optical microscopes.In this work,phototactic microgels with photoresponsive properties are prepared.The microgel particles can be observed by confocal laser scanning microscopy.The photoresponsive properties of microgels are fully investigated by various instruments.Light can also regulate the state of the microgel solution,making it switch between turbidity and clarity.The phototaxis of particles irradiated by UV light was studied,which may be used for microgels enrichment and drug transportation and release.展开更多
Photodetectors based on amorphous InGaZnO(a-IGZO)thin film transistor(TFT)and halide perovskites have attracted attention in recent years.However,such a stack assembly of a halide perovskite layer/an a-IGZO channel,ev...Photodetectors based on amorphous InGaZnO(a-IGZO)thin film transistor(TFT)and halide perovskites have attracted attention in recent years.However,such a stack assembly of a halide perovskite layer/an a-IGZO channel,even with an organic semiconductor film inserted between them,easily has a very limited photoresponsivity.In this article,we investigate photoresponsive characteristics of TFTs by using CsPbX3(X=Br or I)quantum dots(QDs)embedded into the a-IGZO channel,and attain a high photoresponsivity over 10^3A·W^-1,an excellent detectivity in the order of 10^16 Jones,and a light-to-dark current ratio up to 10^5 under visible lights.This should be mainly attributed to the improved transfer efficiency of photoelectrons from the QDs to the a-IGZO channel.Moreover,spectrally selective photodetection is demonstrated by introducing halide perovskite QDs with different bandgaps.Thus,this work provides a novel strategy of device structure optimization for significantly improving the photoresponsive characteristics of TFT photodetectors.展开更多
A chromophoric system 2-(5-(4-dimethylamino-benzylidin)-4-oxo-2-thioxo-thiazoli din-3-yl)acetic acid with push-pull electron modulation was synthesised and incorporated onto lignin core (technical lignin, lignin sulph...A chromophoric system 2-(5-(4-dimethylamino-benzylidin)-4-oxo-2-thioxo-thiazoli din-3-yl)acetic acid with push-pull electron modulation was synthesised and incorporated onto lignin core (technical lignin, lignin sulphonic acid M.W. 52,400) and the photo responsive behaviour was investigated. The product was characterised by UV-visible, fluores-cence, FT-IR, and NMR spectroscopic methods. The results of the studies show that the incorporation of the chromo-phoric system on to the lignin core enhanced the light absorption and light stabilization properties of the chromophoric system. The remarkable stability on irradiation provides a novel photo responsive system with excellent light fastening properties which would find application in coating materials, dyes, paints etc.展开更多
In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-vip interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene...In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-vip interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene （tAzo） group. To link β-CD to the hydrophobic section, renewable EC was used as macroinitiator to initiate the polymerization of ε-caprolactone （ε-CL） to form biocompatible and biodegradable comb copolymer EC-g-PCL, and β-CD was attached to the end of PCL side chain via click reaction. Meanwhile, hydrophilic PEG-tAzo was obtained by N,N＇-dicyclohexylcarbodiimide （DCC） coupling. Then, the structures of the products were characterized by nuclear magnetic resonance （NMR） and gel permeation chromatography （GPC）. Subsequently, with the formation of inclusion complexes by β-CD and tAzo groups, the obtained EC-g-PCL-β-CD/PEG-tAzo supramolecular system self-assembled in water with hydrophobic EC-g-PCL-β-CD as core and hydrophilic PEG-tAzo as shell. Furthermore, dynamic light scattering （DLS） and transmission electron microscopy （TEM） were utilized to investigate the particle size and size distribution, while NMR and UV-Vis spectra were applied to explore the UV-Visible light stimuli-responsiveness of the micelles.展开更多
Compared with the conventional strategies of electronic and/or steric perturbation,catalytic olefin polymerization modulated by light irradiation or metal-metal cooperativity effect is a fascinating challenge that att...Compared with the conventional strategies of electronic and/or steric perturbation,catalytic olefin polymerization modulated by light irradiation or metal-metal cooperativity effect is a fascinating challenge that attracts considerable attention in the academic community.In this context,we design a strategy that could employ both effects to influence the polymerization process.Some dinuclear salicylaldimine andα-imino-ketone nickel complexes bearing a stiff-stilbene bridge were prepared,which could transfer between(E)-isomers and(Z)-isomers under ultraviolet irradiation.This isomerization can tune the electronic,steric and metal-metal cooperativity effects of the nickel catalysts.In this way,the catalytic activity,as well as polymer microstructures including molecular weight and branching density can be modulated in ethylene polymerization and copolymerization reactions.This strategy is generally applicable to other olefin polymerization catalytic systems and other types of transition metal mediated catalysis.展开更多
CONSPECTUS:The concept of photoresponsive coordination polymer(CP)single crystal platforms(CPSCPs)is based on photoresponsive olefin CP single crystals,which can undergo photocycloaddition reactions under light irradi...CONSPECTUS:The concept of photoresponsive coordination polymer(CP)single crystal platforms(CPSCPs)is based on photoresponsive olefin CP single crystals,which can undergo photocycloaddition reactions under light irradiation through a single-crystal-to-single-crystal(SCSC)transformation.Taking advantage of the coordination of olefin ligands to metal ions of Zn^(2+),Cd^(2+),etc.,a pair of C=C double bonds is positioned adjacent to each other in space at a suitable distance and orientation to allow[2+2]photocycloaddition triggered by UV−vis irradiation,affording cyclobutanes in the CPs.The single crystal nature of CPs allows their structures to be determined by X-ray diffraction,providing details of the arrangements in space of the C=C double bonds.These CPs are promising platforms for the synthesis of organic molecules,such as cyclobutanes and derivatives,with high regioselectivity and stereoselectivity without any catalyst.The[2+2]photocycloaddition reactions may induce structural modifications like expansion or shrinking of unit cells,resulting in macroscopic changes(e.g.,cracking,bending,etc.)of the whole CP single crystals and leading to changes in chemical and physical properties.Applications take advantage of their optical properties,including luminescence and absorption,and allow the detection of vip molecules and photomechanical motions.Although much effort has been devoted to such studies,it remains challenging to develop systematic investigations aiming at increasing the diversity of CPs and properties to meet practical needs.Moreover,more efficient methods are desirable to investigate the reaction mechanisms in the solid state and monitor the structural changes occurring during the process.In this Account,we introduce our research on the design and applications of photoresponsive CPSCPs.It is divided into three parts.First,the design and construction of various CPs with different olefin ligands are discussed.Through a suitable and sometimes sophisticated choice of metal ions and auxiliary carboxylate ligands,these olefin ligands meet the requirements to undergo[2+2]photocycloaddition reactions in CP structures,allowing for the precise synthesis of cyclobutanes and their derivatives.These compounds could be subsequently extracted from the CPs to give pure organic products.Second,we introduce new strategies,such as a combination of single crystal X-ray diffraction(SCXRD)with thermal/phototreatments of CPs and in situ fluorescence spectroscopy,to monitor the structural changes occurring on the olefin ligands during the reaction.Furthermore,the fast stepwise photoreaction could also be visualized with high resolution.These data significantly strengthen our understanding of solid-state[2+2]photocycloaddition reactions in CPs.Third,applications of photoresponsive CPs are described,which focus on optical and photoinduced mechanical properties.Considering the optical properties,the conjugated structures of the olefin ligands change during the reactions,and circular dichroism(CD)and fluorescence were used for their detection and imaging.Furthermore,the photoinduced mechanical properties of CPs could be significantly expanded through the combination of CP crystals with polymers.Lastly,we point out the challenges and directions for future research in the field.We hope this Account will provide an overview of research on photoresponsive CPSCPs,attract more attention from the community,and inspire future research.展开更多
Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation...Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously.Herein,we report the construction of a new PMOP(Cu_(24)(C_(16)H_(12)N_(2)O_(4))_(12)(C_(18)H_(22)O_(5))12,denoted as MOP-PR-LA),where long alkyl(LA)chains act as the intermolecular poles,propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive(PR)moieties.Upon ultraviolet(UV)-and visible-light irradiation,MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA.For propylene adsorption,MOP-PR has a low change of adsorption capacity(9.9%),while that of MOP-PR-LA reaches 58.6%.Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption,while the trans state of PR favors adsorption.This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.展开更多
Light-driven actuators are widely used for smart devices such as soft robots.One of the main challenges for actuators is achieving rapid responsiveness,in addition to ensuring favorable mechanical properties.Herein,we...Light-driven actuators are widely used for smart devices such as soft robots.One of the main challenges for actuators is achieving rapid responsiveness,in addition to ensuring favorable mechanical properties.Herein,we focused on photoresponsive polyurethane(CD-Azo-PU)based on controlling the crystallization of the hard segments in polyurethane(PU)by complexation between azobenzene(Azo)and cyclodextrins(CDs).CD-Azo-PU incorporated polyurethane as the main chain and a 1:2 inclusion complex between Azo andγCD as a movable crosslink point.Upon ultraviolet light(UV,λ=365 nm)irradiation,the photoresponsiveness of CD-Azo-PU bent toward the light source(defined as positive),while that of the linear Azo polyurethane(Azo-LPU)without peracetylatedγ-cyclodextrin diol(TAcγCD-diOH)as a movable crosslinker bent in the direction opposite the light source.The bending rates were determined to be 0.25°/s for CD-Azo-PU and 0.083◦/s for Azo-LPU,indicating that the bending rate for CD-Azo-PU was faster than that for Azo-LPU.By incorporating movable crosslinks into CD-Azo-PU,we successfully achieved specific photoresponsive actuation with an enhanced rate.展开更多
pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This pro...pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This property makes invasive pH control can be replaced by noninvasive light control.However,photoacid is rare.In this work,macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp.When the solution of calixpyridinium−disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp,disulfonated xantphos was able to receive the protons released from calixpyridinium.This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function.The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates.Moreover,the photoresponsive disassembly is reversible by heating.This photoresponsive material was further applied as a photocontrolled release model.In addition,a dissipative assembly was successfully designed based on this photoresponsive disassembly.This study supplies a generalized strategy to construct pH-responsive biocompatible materials with light-control properties by using macrocyclic calixpyridinium and its matched various vips in water.展开更多
Selectively controlling the bioactivity of antimicrobial peptides is not only a fascinating scientific challenge but also a necessity in localized antibacterial therapy.Here,a smart antimicrobial system has been fabri...Selectively controlling the bioactivity of antimicrobial peptides is not only a fascinating scientific challenge but also a necessity in localized antibacterial therapy.Here,a smart antimicrobial system has been fabricated via host–vip driven dynamic selfassembly between a branched cyclodextrin and cationic linear peptides appended with azobenzene side chains.The self-assembly structure of the host–vip system could be controlled reversibly through the photoresponsive isomerization of azobenzene moieties.展开更多
Organic photoresponsive materials can undergo various reversible variations in certain physical and chemical properties,such as optical properties,electrochemical properties,conformation,and conductivity,upon photoirr...Organic photoresponsive materials can undergo various reversible variations in certain physical and chemical properties,such as optical properties,electrochemical properties,conformation,and conductivity,upon photoirradiation.They have been widely applied in various optoelectronic fields,especially in information storage.We summarize research progress on organic photoresponsive materials for information storage.First,the design strategies and photoswitching mechanisms for various kinds of organic photoresponsive materials,including small organic molecules,metal complexes,polymers,supramolecules,and cholesteric liquid crystals,are systematically summarized.These materials exhibit reversible changes of absorption and/or emission properties in response to different wavelengths of light.Subsequently,the applications of these organic materials in information storage,such as data(re)writing and erasing,encryption and decryption,and anticounterfeiting,are introduced in detail.Finally,the current challenges and future directions in this rapidly growing research field are discussed.The review will provide important guidance on the future works about the design of excellent organic photoresponsive materials for optoelectronic applications.展开更多
基金supported by grants from the National Natural Science Foundation of China(Nos.22273037,21731003)。
文摘Metal-organic frameworks(MOFs)containing face-to-faceπ-πinteracting anthracene groups are promising photoresponsive materials because of their rich photophysical properties and their ability to undergo reversible[4+4]photocycloaddition reaction,but it is extremely challenging to obtain such materials.Herein,we propose a generalized method to accomplish photoresponsive MOFs by introducing anthracene pairs into the framework of the dianthracene-phosphonate-based MOFs by controlling the synthesis temperature.Compounds Dy_(2)(ampH)_(2x)(amp2H_(2))_(3-x)(H_(2)O)_(6)·4H_(2)O[x=0.01,Dy-70;x=0.02,Dy-80;x=0.037,Dy-90;amp_(2)H_(4)=pre-photodimerized 9-anthracenemethylphosphonic acid(amp H_(2))]were obtained by the reaction of DyCl_(3)and amp_(2)H_(4)in water at 70,80,and 90℃,respectively.They all show excimer emission of paired anthracenes at ca.555 nm.Detailed studies of Dy-90 have shown that it undergoes a reversible photodimerization reaction under 365 nm and then 280 nm illumination,accompanied by luminescence changes.This property further enables Dy-90 to be used for optical anti-counterfeiting.
基金financially supported by the National Natural Science Foundation of China(Nos.22435005,22193042,21921001,52202194,22305105,22201284)the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(No.ZDBSLY-SLH024)。
文摘Two-dimensional(2D)organic-inorganic hybrid perovskites(OIHPs)have been developed as promising candidates for photodetection,owing to their excellent semiconducting features and structural tunability.However,as an important parameter for photodetection,the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations,constraining their further development.The emerging aromatic amine-based alternating-cations-interlayered(A-ACI)hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability,provide an extra solution for achieving ideal photoresponsive range.Herein,for the first time,the photoresponsive range is successfully broadened in A-ACI hybrid perovskites(NMA)_(4)(FA)_(2)Pb_(3)Br_(12)(2)remolding from(NMA)_(4)(MA)_(2)Pb_(3)Br_(12)(1)(NMA=N-methylbenzylaminium,FA=formamidinium and MA=methylammonium).Particularly,1 and 2adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner.Importantly,2 exhibits a narrower bandgap than 1,which can be ascribed to the lowlying conduct band composed of intercalation FAπ*orbitals.Meanwhile,2 possesses a shorter interlayer distance and flatter inorganic skeleton,synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range(70 nm).This research not only enriches the perovskite family but also provides insights into structure-property relationships.
基金supported by the Topnotch Talents Program of Henan Agricultural University(30501032,30500418,30501049)the National Natural Science Foundation of China(22305070,U20041101)+2 种基金the Natural Science Foundation of Henan Province(232300420132)the Scientific and Technological Project of the Henan Province(222102240043)the Distinguished Young Scholar Fund Project of Hunan Province Natural Science Foundation(2023JЛ10041)。
文摘Photoresponsive smart materials,which exhibit swift or instantaneous responses to external light stimuli,are pivotal for advancing the development of novel smart devices.Among these materials,photoresponsive tetracoordinate arylboron com-pounds emerge as prominent molecular systems,owing to their captivating photochemical mechanisms and photophysical transformations.In recent years,these molecules have experienced notable progress,leading to the emergence of numerous organic boron photoresponsive molecular systems with innovative structures and exceptional performance.In this comprehensive review,we present a thorough examination of the latest advancements in the field,systematically elucidating the design strategies and structure-activity relationships of these mol-ecules.Furthermore,we delve into the photoresponse mechanisms of various molecules and summarize their unique characteristics.Ultimately,we analyze the challenges,opportunities,and prospects encountered in this exciting field of research.
基金financially supported by the Alexander von Humboldt Foundation(postdoc stipend to X.Q.Dou)the European Research Council(No.279202)the National Natural Science Foundation of China(Nos.51833006 and 51573092)
文摘Photoresponsive hydrogels have been attractive because they can provide precise spatial and temporal control for molecule release, whereas the conventional preparation of photoresponsive hydrogels generally involves complex chemical synthesis steps or specific conditions which limits their practical applications. Herein, a new photoresponsive hydrogel is facilely prepared via co-assembly of two simple molecules, Fmoc-Phe-OH and Azp, without chemical synthesis. The co-assembly mechanism, morphology, and photoresponsiveness of(Fmoc-Phe-OH)-Azp hydrogel are investigated by circular dichroism(CD), ultraviolet-visible(UV-Vis), fluorescence, ~1 H nuclear magnetic resonance(~1 H-NMR), attenuated total internal reflection Fourier transform Infrared(ATR-FTIR) spectroscopy, and scanning electron microscopy(SEM). Furthermore, the enhanced release of encapsulated sulforhodamine B(SRB) dye molecules can be achieved via UV light irradiation. The enhanced dye release amount can be controlled by manipulating photoirradiation time. This study provides a facile way to prepare photoresponsive hydrogel which holds great potential for controllable drug release.
基金State Key Laboratory of Natural and Biomimetic Drugs and Peking University(bmu2009137-121)
文摘For the main purpose of manipulating the functions of molecules, researchers have made great achievements on photoresponsive molecules using light as a trigger. Light has become a promising scientific tool due to it being a clean and noninvasive external stimulant. By attachment of photoresponsive moieties to molecules, the biological activities of molecules can be attenuated by light activation. With wide applications of laser in life sciences, it will be possible to achieve high spatiotemporal resolution. In this review, we focus on photoresponsive nucleic acids for photomodulating gene expression with light activation. With incorporation of photoswitchable or photocleavable moieties, biological behaviors of nucleic acids are photoregulated reversibly or irreversibly. Recent development and applications of photoresponsive nucleic acid in vitro and in vivo have shown a very promising future for manipulation of specific functional genes or disease genes. We expect that photoresponsive nucleic acids will be powerful scientific tools for studying biological events as well as gene therapy agents for genetic diseases.
基金financially supported by the National Natural Science Foundation of China for Science Center Program (No. 21788102)Creative Research Groups (No. 21421004)+4 种基金Key Project (No. 21636002)Shanghai Pujiang Program (No. 20PJ1402900)National key Research and Development Program (No. 2016YFA0200300)Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)Program of Introducing Talents of Discipline to Universities (No. B16017)。
文摘The development of solid-state smart materials, in particular those showing photoresponsive luminescence, is highly desirable for their cutting edge applications in displays, sensors, data-storage, and anticounterfeiting. However, to achieve both excellent photoresponsive performance and bright luminescence in solid state remains challenge. Herein, we integrate a novel photochromic fluorophore YL into flexible polymer chains, thereby enabling the resultant polymer PYL with reversible photoisomerization upon aggregation. Remarkably, the polymer PYL possesses excellent photochromic properties and aggregationinduced emission(AIE) activity, which can be attributed to the photoactive YL moiety. Upon light exposure, its film exhibits reversibly off-to-on fluorescent modulation with quick response, high emission efficiency and signal contrast, sharply different from the weak emission in solution. The novel photoresponsive AIE polymer with invisible/visible color and fluorescence transformation allows for advanced anti-counterfeiting applications. This work provides an efficient platform for constructing solid-state photocontrollable luminescent materials.
基金financial supported by National Natural Science Foundation of China (Nos. 21372079, 21472046)Shanghai Pujiang Program (No. 14PJD012)the Fundamental Research Funds for the Central Universities (No. 222201414015)
文摘A series of imidacloprid derivatives containing an azopyridine motif as a photoswitchable functional group were designed and synthesized. The new version of photoresponsive imidacloprid analogues showed improved solubility in comparison with their azobenzene analogues. 1.2 to 2-fold activity difference was observed for these azopyridine-imidacloprids against house fly （Musca domestica） and cowpea aphid （Aphis craccivora） upon irradiation.
基金supported financially by the National Natural Science Foundation of China(Nos.21302212 and 21522209)the "Strategic Priority Research Program"(No.XDB12010100)
文摘In recent years,organic field-effect transistors（OFETs） with high performance and novel multifunctionalities have attracted considerable attention.Meanwhile,featured with reversible photoisomerization and the corresponding variation in color,chemical/physical properties,photochromic molecules have been applied in sensors,photo-switches and memories.Incorporation of photochromic molecules to blend in the device functional layers or to modify the interfaces of OFETs is common way to build photo-transistors.In this review,we focus on the recent advantages on the study of photoresponsive transistors involving one of three typical photochromic compounds spiropyran,diarylethene and azobenzene.Three main strategies are demonstrated in detail.Firstly,photochromic molecules are doped in active layers or combined with semiconductor structure thus forming photoreversible active layers.Secondly,the modification of dielectric layer/active layer interface is mainly carried out by bilayer dielectric.Thirdly,the photo-isomerization of self-assembled monolayer（SAM） on the electrode/active layer interface can reversibly modulate the work functions and charge injection barrier,result in bifunctional OFETs.All in all,the combination of photochromic molecules and OFETs is an efficient way for the fabrication of organic photoelectric devices.Photoresponsive transistors consisted of photochromic molecules are potential candidate for real applications in the future.
基金This work was supported by National Natural Foundation of China (No. 59873013).
文摘Several kinds of novel azobenzene-containing polyelectrolytes with special molecular design have been developed from acryloyl chloride or epoxy based precursor polymers. The acryloyl chloride based precursor polymer, poly(acryloyl chloride), was prepared by free radical polymerization of acryloyl chloride. The azo polyelectrolytes were prepared by an esterification reaction between the precursor polymer and corresponding azo chromophores containing a reactive hydroxyl group, followed by hydrolysis of the unreacted acyl chloride groups. The epoxy based precursor polymer was prepared by the reaction between 1,4-cyclohexanedimethanol diglycidyl ether and aniline, and postfunctionalized by azo coupling reaction to form azo polymers containing chromophores with ionizable groups. The polyelectrolytes were characterized by elemental analysis, H-1-NMR, IR and UV-Vis spectroscopy. The photodynamic and photoresponsive properties, as well as self-assembly of these azo polyelectrolytes are reported in this paper([1]).
基金supported by the National Natural Science Foundation of China(No.21274135,No.21871243 and No.51673181)。
文摘Smart functional microgels hold great potential in a variety of applications,especially in drug transportation.However,current drug carriers based on physiological internal stimuli cannot efficiently orientate to designated locations.Therefore,it is necessary to introduce the self-propelled particles to the drug release of the microgels.In order to study self-propulsion of microgels induced by light,it is also a challenge to prepare micronsized microgels so that they can be observed directly under optical microscopes.In this work,phototactic microgels with photoresponsive properties are prepared.The microgel particles can be observed by confocal laser scanning microscopy.The photoresponsive properties of microgels are fully investigated by various instruments.Light can also regulate the state of the microgel solution,making it switch between turbidity and clarity.The phototaxis of particles irradiated by UV light was studied,which may be used for microgels enrichment and drug transportation and release.
基金Project supported by the National Natural Science Foundation of China(Grant No.61874029)the National Key Technologies R&D Program of China(Grant No.2015ZX02102-003).
文摘Photodetectors based on amorphous InGaZnO(a-IGZO)thin film transistor(TFT)and halide perovskites have attracted attention in recent years.However,such a stack assembly of a halide perovskite layer/an a-IGZO channel,even with an organic semiconductor film inserted between them,easily has a very limited photoresponsivity.In this article,we investigate photoresponsive characteristics of TFTs by using CsPbX3(X=Br or I)quantum dots(QDs)embedded into the a-IGZO channel,and attain a high photoresponsivity over 10^3A·W^-1,an excellent detectivity in the order of 10^16 Jones,and a light-to-dark current ratio up to 10^5 under visible lights.This should be mainly attributed to the improved transfer efficiency of photoelectrons from the QDs to the a-IGZO channel.Moreover,spectrally selective photodetection is demonstrated by introducing halide perovskite QDs with different bandgaps.Thus,this work provides a novel strategy of device structure optimization for significantly improving the photoresponsive characteristics of TFT photodetectors.
文摘A chromophoric system 2-(5-(4-dimethylamino-benzylidin)-4-oxo-2-thioxo-thiazoli din-3-yl)acetic acid with push-pull electron modulation was synthesised and incorporated onto lignin core (technical lignin, lignin sulphonic acid M.W. 52,400) and the photo responsive behaviour was investigated. The product was characterised by UV-visible, fluores-cence, FT-IR, and NMR spectroscopic methods. The results of the studies show that the incorporation of the chromo-phoric system on to the lignin core enhanced the light absorption and light stabilization properties of the chromophoric system. The remarkable stability on irradiation provides a novel photo responsive system with excellent light fastening properties which would find application in coating materials, dyes, paints etc.
基金financially supported by the National Natural Science Foundation of China(Nos.21174076 and 21374053)the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20120002110015)
文摘In this work, a UV-Visible light controlled supramolecular system based on ethyl cellulose （EC） was constructed, combining the host-vip interaction of β-cyclodextrin （β-CD） group and trans-isomer of azobenzene （tAzo） group. To link β-CD to the hydrophobic section, renewable EC was used as macroinitiator to initiate the polymerization of ε-caprolactone （ε-CL） to form biocompatible and biodegradable comb copolymer EC-g-PCL, and β-CD was attached to the end of PCL side chain via click reaction. Meanwhile, hydrophilic PEG-tAzo was obtained by N,N＇-dicyclohexylcarbodiimide （DCC） coupling. Then, the structures of the products were characterized by nuclear magnetic resonance （NMR） and gel permeation chromatography （GPC）. Subsequently, with the formation of inclusion complexes by β-CD and tAzo groups, the obtained EC-g-PCL-β-CD/PEG-tAzo supramolecular system self-assembled in water with hydrophobic EC-g-PCL-β-CD as core and hydrophilic PEG-tAzo as shell. Furthermore, dynamic light scattering （DLS） and transmission electron microscopy （TEM） were utilized to investigate the particle size and size distribution, while NMR and UV-Vis spectra were applied to explore the UV-Visible light stimuli-responsiveness of the micelles.
基金supported by the National Natural Science Foundation of China(22471247,U1904212 and U2004191)the Natural Science Foundation of Henan Province(202300410477 and 222300420294)the China Postdoctoral Science Foundation(2020 M672260).
文摘Compared with the conventional strategies of electronic and/or steric perturbation,catalytic olefin polymerization modulated by light irradiation or metal-metal cooperativity effect is a fascinating challenge that attracts considerable attention in the academic community.In this context,we design a strategy that could employ both effects to influence the polymerization process.Some dinuclear salicylaldimine andα-imino-ketone nickel complexes bearing a stiff-stilbene bridge were prepared,which could transfer between(E)-isomers and(Z)-isomers under ultraviolet irradiation.This isomerization can tune the electronic,steric and metal-metal cooperativity effects of the nickel catalysts.In this way,the catalytic activity,as well as polymer microstructures including molecular weight and branching density can be modulated in ethylene polymerization and copolymerization reactions.This strategy is generally applicable to other olefin polymerization catalytic systems and other types of transition metal mediated catalysis.
基金supported by the National Natural Science Foundation of China(Grant Nos.U24A20507,22271203,and 22301204)the State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences(Grant No.2024KF005)+1 种基金Open Research Fund of State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,the Collaborative Innovation Centre of Suzhou Nano Science and Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions,the Project of Scientific and Technologic Infrastructure of Suzhou(Grant No.SZS201905)Soochow University Starting Grant(No.NH10902124 to Q.L.).
文摘CONSPECTUS:The concept of photoresponsive coordination polymer(CP)single crystal platforms(CPSCPs)is based on photoresponsive olefin CP single crystals,which can undergo photocycloaddition reactions under light irradiation through a single-crystal-to-single-crystal(SCSC)transformation.Taking advantage of the coordination of olefin ligands to metal ions of Zn^(2+),Cd^(2+),etc.,a pair of C=C double bonds is positioned adjacent to each other in space at a suitable distance and orientation to allow[2+2]photocycloaddition triggered by UV−vis irradiation,affording cyclobutanes in the CPs.The single crystal nature of CPs allows their structures to be determined by X-ray diffraction,providing details of the arrangements in space of the C=C double bonds.These CPs are promising platforms for the synthesis of organic molecules,such as cyclobutanes and derivatives,with high regioselectivity and stereoselectivity without any catalyst.The[2+2]photocycloaddition reactions may induce structural modifications like expansion or shrinking of unit cells,resulting in macroscopic changes(e.g.,cracking,bending,etc.)of the whole CP single crystals and leading to changes in chemical and physical properties.Applications take advantage of their optical properties,including luminescence and absorption,and allow the detection of vip molecules and photomechanical motions.Although much effort has been devoted to such studies,it remains challenging to develop systematic investigations aiming at increasing the diversity of CPs and properties to meet practical needs.Moreover,more efficient methods are desirable to investigate the reaction mechanisms in the solid state and monitor the structural changes occurring during the process.In this Account,we introduce our research on the design and applications of photoresponsive CPSCPs.It is divided into three parts.First,the design and construction of various CPs with different olefin ligands are discussed.Through a suitable and sometimes sophisticated choice of metal ions and auxiliary carboxylate ligands,these olefin ligands meet the requirements to undergo[2+2]photocycloaddition reactions in CP structures,allowing for the precise synthesis of cyclobutanes and their derivatives.These compounds could be subsequently extracted from the CPs to give pure organic products.Second,we introduce new strategies,such as a combination of single crystal X-ray diffraction(SCXRD)with thermal/phototreatments of CPs and in situ fluorescence spectroscopy,to monitor the structural changes occurring on the olefin ligands during the reaction.Furthermore,the fast stepwise photoreaction could also be visualized with high resolution.These data significantly strengthen our understanding of solid-state[2+2]photocycloaddition reactions in CPs.Third,applications of photoresponsive CPs are described,which focus on optical and photoinduced mechanical properties.Considering the optical properties,the conjugated structures of the olefin ligands change during the reactions,and circular dichroism(CD)and fluorescence were used for their detection and imaging.Furthermore,the photoinduced mechanical properties of CPs could be significantly expanded through the combination of CP crystals with polymers.Lastly,we point out the challenges and directions for future research in the field.We hope this Account will provide an overview of research on photoresponsive CPSCPs,attract more attention from the community,and inspire future research.
基金the National Key R&D Program of China(No.2022YFB3806800)the National Science Fund for Distinguished Young Scholars(No.22125804)+1 种基金the National Natural Science Foundation of China(No.22078155)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Photoresponsiveness of materials is critical to their tunability and efficiency in terminal applications.Photoresponsive metal-organic polyhedra(PMOPs)feature intrinsic pores and remote controllability,but aggregation of PMOPs in solid state hampers their photoresponsiveness seriously.Herein,we report the construction of a new PMOP(Cu_(24)(C_(16)H_(12)N_(2)O_(4))_(12)(C_(18)H_(22)O_(5))12,denoted as MOP-PR-LA),where long alkyl(LA)chains act as the intermolecular poles,propping against adjacent PMOP molecules to create individual microenvironment benefiting the isomerization of photoresponsive(PR)moieties.Upon ultraviolet(UV)-and visible-light irradiation,MOP-PR-LA is much easier to isomerize than the counterpart MOP-PR without LA.For propylene adsorption,MOP-PR has a low change of adsorption capacity(9.9%),while that of MOP-PR-LA reaches 58.6%.Density functional theory calculations revealed that PR in the cis state has a negative effect on adsorption,while the trans state of PR favors adsorption.This work might open an avenue for the construction of photoresponsive materials with high responsiveness and controllability.
基金MEXT of Japan,Grant/Award Numbers:JP19H05714,JP19H05721Core Research for Evolutional Science and Technology(CREST),Grant/Award Number:JPMJCR22L4+4 种基金Establishment of university fellowships toward the creation of science technology innovation,Grant/Award Number:JPMJFS2125Iketani Science and Technology Foundation,Grant/Award Numbers:0341026-A,0351026-AAsahi Glass FoundationYazaki Memorial Foundation for ScienceCOI-NEXT program,Grant/Award Number:JPMJPF2218。
文摘Light-driven actuators are widely used for smart devices such as soft robots.One of the main challenges for actuators is achieving rapid responsiveness,in addition to ensuring favorable mechanical properties.Herein,we focused on photoresponsive polyurethane(CD-Azo-PU)based on controlling the crystallization of the hard segments in polyurethane(PU)by complexation between azobenzene(Azo)and cyclodextrins(CDs).CD-Azo-PU incorporated polyurethane as the main chain and a 1:2 inclusion complex between Azo andγCD as a movable crosslink point.Upon ultraviolet light(UV,λ=365 nm)irradiation,the photoresponsiveness of CD-Azo-PU bent toward the light source(defined as positive),while that of the linear Azo polyurethane(Azo-LPU)without peracetylatedγ-cyclodextrin diol(TAcγCD-diOH)as a movable crosslinker bent in the direction opposite the light source.The bending rates were determined to be 0.25°/s for CD-Azo-PU and 0.083◦/s for Azo-LPU,indicating that the bending rate for CD-Azo-PU was faster than that for Azo-LPU.By incorporating movable crosslinks into CD-Azo-PU,we successfully achieved specific photoresponsive actuation with an enhanced rate.
基金We thank the Natural Science Foundation of Tianjin City(20JCYBJC00330)for financial support.
文摘pH is an important stimuli-responsive signal because deprotonation-protonation process is crucial for many life functions.Photoacid is a kind of photoresponsive group that can release protons upon irradiation.This property makes invasive pH control can be replaced by noninvasive light control.However,photoacid is rare.In this work,macrocyclic calixpyridinium was found to be used as a photoacid to release protons from acidic methylene under the irradiation of a 254 nm UV lamp.When the solution of calixpyridinium−disulfonated xantphos aggregates were irradiated by a 254 nm portable UV lamp,disulfonated xantphos was able to receive the protons released from calixpyridinium.This noninvasive photocontrolled proton transfer not only replaces an invasive pH regulation but also achieves a synergistic function.The deprotonation of calixpyridinium and the protonation of disulfonated xantphos can occur simultaneously to disrupt the aggregates.Moreover,the photoresponsive disassembly is reversible by heating.This photoresponsive material was further applied as a photocontrolled release model.In addition,a dissipative assembly was successfully designed based on this photoresponsive disassembly.This study supplies a generalized strategy to construct pH-responsive biocompatible materials with light-control properties by using macrocyclic calixpyridinium and its matched various vips in water.
基金supported by the National Natural Science Foundation of China(NSFC21822201 and 21573091).
文摘Selectively controlling the bioactivity of antimicrobial peptides is not only a fascinating scientific challenge but also a necessity in localized antibacterial therapy.Here,a smart antimicrobial system has been fabricated via host–vip driven dynamic selfassembly between a branched cyclodextrin and cationic linear peptides appended with azobenzene side chains.The self-assembly structure of the host–vip system could be controlled reversibly through the photoresponsive isomerization of azobenzene moieties.
基金This work was supported by the National Funds for Distinguished Young Scientists(61825503)the National Natural Science Foundation of China(61775101)the Priority Academic Program Development of Jiangsu Higher Education Institutions(YX030003).
文摘Organic photoresponsive materials can undergo various reversible variations in certain physical and chemical properties,such as optical properties,electrochemical properties,conformation,and conductivity,upon photoirradiation.They have been widely applied in various optoelectronic fields,especially in information storage.We summarize research progress on organic photoresponsive materials for information storage.First,the design strategies and photoswitching mechanisms for various kinds of organic photoresponsive materials,including small organic molecules,metal complexes,polymers,supramolecules,and cholesteric liquid crystals,are systematically summarized.These materials exhibit reversible changes of absorption and/or emission properties in response to different wavelengths of light.Subsequently,the applications of these organic materials in information storage,such as data(re)writing and erasing,encryption and decryption,and anticounterfeiting,are introduced in detail.Finally,the current challenges and future directions in this rapidly growing research field are discussed.The review will provide important guidance on the future works about the design of excellent organic photoresponsive materials for optoelectronic applications.
