Doping perylene diimide(PDI)into a polymer matrix is a simple strategy to prepare near-infrared(NIR)reflective materials,but the mechanical properties and NIR reflectance properties are significantly compromised due t...Doping perylene diimide(PDI)into a polymer matrix is a simple strategy to prepare near-infrared(NIR)reflective materials,but the mechanical properties and NIR reflectance properties are significantly compromised due to macro-phase separation.In this study,a novel polymer(denoted as PU-PDI)with intrinsic NIR reflective proper⁃ties was synthesized by covalent incorporation of PDI units into polyurethane chains.Its photophysical characteris⁃tics,mechanical property and NIR reflectance property are investigated in detail.The results show that covalent in⁃corporation reduces the severe aggregation of PDI units,thereby endows PU-PDI with excellent mechanical property.The elongation at break of PU-PDI can reach more than 700%,and the breaking strength is 34.11 MPa.Moreover,compared to the blending system,PU-PDI possesses enhanced NIR reflection ability due to the better dispersion of PDI units.展开更多
Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using l...Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using linear-shaped ligands have not yet been explored.Herein,we present the design of NUT-123 by incorporating a near-linear perylene diimide(PDI)derivate,PDI-CH_(3)-COOH,into the preselected zirconium-based MOLs.3D electron diffraction confirms the successful construction of a novel topology in NUT-123.Furthermore,the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI-CH_(3)-COOH.NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility,achieving 100%conversion of various organic sulfides.Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer.This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.展开更多
Organic electrodes are considered competitive candidates for the next-generation high-performance energy storage devices owing to their advantages of structural flexibility and abundant resources.However,solubility an...Organic electrodes are considered competitive candidates for the next-generation high-performance energy storage devices owing to their advantages of structural flexibility and abundant resources.However,solubility and low electronic conductivity have been major obstacles to the practical application.To address these challenges,the structural design and interfacial regulation of organic electrodes are crucial to the performance enhancement.Herein,we report on aπ-conjugated polymer cathode material of poly(3,4,9,10-perylenetetracarboxylic diimide)(PPI)for metal ion batteries,and the performance optimization is achieved by matching suitable conductive carbons and liquid electrolytes.Ultimately,the carbon nanotubes(CNTs)with weight content of 25%and 1 M NaPF6 in ethylene carbonate/diethyl carbonate electrolyte are introduced to assemble the batteries,and the discharge specific capacity,cycling stability and rate performance are enhanced effectively.The PPI-CNTjjNa battery displays high specific capacities of 146.4 and 117 mAh g^(-1) at current densities of 0.1 C and 5 C,respectively.Furthermore,PPI-CNTjjNa battery demonstrates excellent long-term cycling stability of 5000 cycles with low 0.007 mAh g^(-1)capacity decay per cycle at 1C due to the thin and uniform cathode electrolyte interphase.Moreover,the PPI-CNTjjNa battery presents good cycling stability at high temperatures of 60℃,and retains a capacity of 132.5 mAh g^(-1) after 300 cycles with a high capacity retention rate of 96.9%.Besides,PPI-CNT displays good electrochemical performance and compatibility in lithium-ion and potassium-ion batteries.This work provides an alternative optimization strategy for organic electrodes applied in long-lifetime metal ion batteries.展开更多
Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.H...Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.展开更多
Radical anions of electron-deficient perylene diimides(PDI)are attractive near-infrared(NIR)absorbers for photothermal conversion;however,their stability is often compromised by strong aggregation and reoxidation in a...Radical anions of electron-deficient perylene diimides(PDI)are attractive near-infrared(NIR)absorbers for photothermal conversion;however,their stability is often compromised by strong aggregation and reoxidation in air.Herein,we present a class of bacterial composites hybridized with a newly synthesized doubly-strapped PDI cyclophane,termed“Gemini Box”(GBox-3^(4+)),which features air-stable PDI radicals for NIR photothermal conversion.The effective spatial isolation provided by the double-sided cationic molecular straps allows GBox-3^(4+)to completely suppress chromophore aggregation,even in concentrated aqueous solutions up to 2 mmol/L,thereby preserving its characteristic fluorescence for live-cell imaging.After incubation of bacteria with GBox-3^(4+),the radical species PDI·-have been found to stably exist in the bacterial composites under ambient conditions,both in aqueous suspension and solid forms.Further experiments demonstrate that the air stability of the radical species relies on the simultaneous presence of the doubly-strapped PDI dye and the bacteria.Moreover,the dye-bacterial composites exhibited an high-efficiency NIR photothermal effect with high durability,enabling their application as photothermal agents for seawater desalination.This work provides a new access to the in situ fabrication of photothermal materials from biomass,relying on the rational molecular design and the unique microenvironment of bacteria.展开更多
Regioselevtive functionalization of perylene diimides(PDIs)at bay area often requires multistep synthesis and strenuous recrystallization.Direct bromination of perylene diimides only afford the 1,6 and 1,7-regioisomer...Regioselevtive functionalization of perylene diimides(PDIs)at bay area often requires multistep synthesis and strenuous recrystallization.Direct bromination of perylene diimides only afford the 1,6 and 1,7-regioisomers.More importantly,the 1,6-dibromo regioisomers could only be separated by preparative HPLC.Herein,we report a promising strategy for constructing Janus backbone of BN-doped perylene diimide derivatives.This Janus-type configuration results in the unique regioselective functionalization of BN-JPDIs,which yields exclusively the 1,6-regioisomers.Further investigation shows that the Janus-type configuration leads to a net dipole moment of 1.94 D and intramolecular charge transfer,which causes substantial changes on the optoelectronic properties.Moreover,the single crystal organic field-effect transistors based on BN-JPDIs exhibit electron mobilities up to 0.57 cm^(2)V^(-1)s^(-1),showcasing their potential as versatile building block towards high-performance n-type organic semiconductors.展开更多
Compared to organic thin films,organic single crystals offer significant potential in organic phototransistors(OPTs)due to their enhanced charge transport,large surface area,and defect-free nature.However,the developm...Compared to organic thin films,organic single crystals offer significant potential in organic phototransistors(OPTs)due to their enhanced charge transport,large surface area,and defect-free nature.However,the development of n-type semiconductors has lagged behind p-type semiconductors.To enhance semiconductor device performance,a doping process can be employed,which typically involves the introduction of charged impurities into the crystalline semiconducting material.Its aim is to reduce the Ohmic losses,increase carrier density,improve transport capabilities,and facilitate effective carrier injection,ultimately enhancing the electrical properties of the material.Traditional doping processes,however,often pose a risk of damaging the structure of single crystals.In this study,we have synthesized novel cyanosubstituted chiral perylene diimides,which self-assemble into two-dimensional single crystals that can be used for n-type semiconductor devices.We have employed a surface doping strategy using diethylamine vapor without disrupting the crystal structure.The fabricated devices exhibit significantly higher charge transport properties after doping,achieving a maximum electron mobility of 0.14 cm^(2)V^(-1)s^(-1),representing an improvement of over threefold.Furthermore,the optoelectronic performance of the doped devices has significantly improved,with the external quantum efficiency increased by over 9 times and the significantly improved response time.These results suggest that our surface doping technology is a promising way for enhancing the performance of 2D organic single-crystal OPTs.展开更多
The first example of metal Sn-fused perylene diimides(PDI)derivative(Sn-PDI)was designed,synthesized,and investigated.To obtain this type compound,a simple one-pot synthesis,named stannylative cycloaddition reaction,h...The first example of metal Sn-fused perylene diimides(PDI)derivative(Sn-PDI)was designed,synthesized,and investigated.To obtain this type compound,a simple one-pot synthesis,named stannylative cycloaddition reaction,has been successfully developed via a palladium-based catalyst system.The novel mechanism exhibits that the reaction experiences oxidative addition,Pd-cyclization,stannylation,Pd-Sn-cyclization,and reductive elimination processes successively.This stannylative cycloaddition does realize uniqueσ-πhyperconjugation effect and therefore significantly influencing on the photophysical,electrochemical and excited state properties.Compared with those of PDI,both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm.The electron energy levels of Sn-PDI have changed with an uncommon regulation.And Sn-PDI gives a considerably raised highest occupied molecular orbital(HOMO)level of-6.00 eV More importantly,the singlet excitons of Sn-PDI could efficiently intersystem cross(ISC)into triplet state with a long lifetime of 17.8μs,which is far longer than that(4.4 ns)of PDI.展开更多
Two polymers containing （E）-2,3-bis（thiophen-2-yl）acrylonitrile （CNTVT） as a donor unit, perylene diimide （PDI） or naphthalene diimide （NDI） as an acceptor unit, are synthesized by the Stille coupling copoly...Two polymers containing （E）-2,3-bis（thiophen-2-yl）acrylonitrile （CNTVT） as a donor unit, perylene diimide （PDI） or naphthalene diimide （NDI） as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells （OSCs）. Both polymers exhibit broad absorption in the region of 300-850 nm. The LUMO energy levels of the resulted polymers are ca. -3.93 eV and the HOMO energy levels are -5.97 and -5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency （PCE） of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.展开更多
As an emerging organic semiconductor,perylene diimide(PDI)self-assembly has attracted tremendous attention in the aspects of solar cells,sensors,fluorescence probes and n-transistors,etc.In term of photocatalysis,vari...As an emerging organic semiconductor,perylene diimide(PDI)self-assembly has attracted tremendous attention in the aspects of solar cells,sensors,fluorescence probes and n-transistors,etc.In term of photocatalysis,various photocatalysts based on PDI self-assembly exhibit some unique properties,such as intrinsicΠ-Πstacking structure,fast internal charge transfer,band-like electronic structure,flexible structural modifiability,well-defined morphological adjustability and excellent light absorption.This paper mainly presents recent progress on PDI self-assembly regarding how to regulate the electronic structure of PDI self-assembly.In addition,the photocatalytic applications of PDI self-assembly and its complexes were reviewed,such as environmental remedy,energy productions,organic synthesis and photodynamic/photothermal therapy,further highlighting related photocatalytic mechanisms.Finally,the review contents and some perspectives on photocatalytic research of PDI selfassembly were summarized,and some key scientific problems were put forward to direct related photocatalytic research in future.展开更多
We present here a series of perylene diimide(PDI)based isomeric conjugated polymers for the application as efficient electron acceptors in all-polymer solar cells(all-PSCs).By copolymerizing PDI monomers with 1,4-diet...We present here a series of perylene diimide(PDI)based isomeric conjugated polymers for the application as efficient electron acceptors in all-polymer solar cells(all-PSCs).By copolymerizing PDI monomers with 1,4-diethynylbenzene(para-linkage)and 1,3-diethynylbenzene(meta-linkage),isomeric PDI based conjugated polymers with parallel and non-parallel PDI units inside backbones were obtained.It was found that para-linked conjugated polymer(PA)showed better solubility,strongerπ-πstacking,more favorable blend morphology,and better photovoltaic performance than those of meta-linked conjugated polymers(PM)did.Device based on PTB7-Th:PA(PTB7-Th:poly{4,8-bis[5-(2-ethylhexyl)-thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophene-4,6-diyl})showed significantly enhanced photovoltaic performance than that of PTB7-Th:MA(3.29%versus 0.92%).Moreover,the photovoltaic performance of these polymeric acceptors could be further improved via a terpolymeric strategy.By copolymerizing a small amount of meta-linkages into PA,the optimized terpolymeric acceptors enabled to enhance photovoltaic performance with improved the short-circuit current density(Jsc)and fill factor(FF),resulting in an improved power conversion efficiency(PCE)of 4.03%.展开更多
The recyclable and stable ZnFe_(2)O_(4) small particle decorated one‐dimensional perylene diimide(PDI)S‐scheme heterojunction(1D PDI/ZnFe_(2)O_(4))is prepared by the hydrochloric acid‐mediated(HCl‐mediated)strateg...The recyclable and stable ZnFe_(2)O_(4) small particle decorated one‐dimensional perylene diimide(PDI)S‐scheme heterojunction(1D PDI/ZnFe_(2)O_(4))is prepared by the hydrochloric acid‐mediated(HCl‐mediated)strategy,interestingly,the morphology of the 1D PDI/ZnFe_(2)O_(4) can also be effectively regulated by HCl‐mediated process,the existence of HCl can regulate PDI into a uniform rod structure,while the co‐existence of HCl and PDI can limit ZnFe_(2)O_(4) to become the uniform small particles.More importantly,based on the 1D rod structure of PDI and the small size effect of ZnFe_(2)O_(4),carriers can migrate to the surface more easily,which can improve the photocatalytic activity.Meanwhile,due to the appropriate energy level structure,the S‐scheme heterojunction structure is formed between PDI and ZnFe_(2)O_(4),which eliminates meaningless photo‐generated charge carriers through recombination and introduces strong redox to further enhance the photodegradation effect,thereby,1D PDI/ZnFe_(2)O_(4) exhibits excellent photocatalytic ability,under the visible light irradiation,the degradation rate of tetracycline(TC)with 1D PDI/ZnFe_(2)O_(4)(66.67%)is 9.18 times that with PDI(7.26%)and 9.73 times that with ZnFe_(2)O_(4)(6.85%).This work proposes new ideas for the assembly of magnetic organic‐inorganic S‐scheme heterojunction photocatalysts.展开更多
The consecutive two‐photon photocatalytic behavior of perylene diimide(PDI)enables it to catalyze photoreduction reactions that are thermodynamically unfavorable via single‐photon processes.In this work,we developed...The consecutive two‐photon photocatalytic behavior of perylene diimide(PDI)enables it to catalyze photoreduction reactions that are thermodynamically unfavorable via single‐photon processes.In this work,we developed a heterogeneous PDI photocatalyst by covalently binding PDI molecules on the surface of nanosilica.This photocatalyst structure overcomes the intrinsic limitation of the low solubility of PDI,but retains its consecutive two‐photon photocatalytic property.Detailed characterization of the photocatalyst by techniques such as thermogravimetric analysis,solid‐state nuclear magnetic resonance spectroscopy,and Fourier transform infrared spectroscopy indicated that the PDI molecules were anchored covalently on the surface of nanosilica.The obtained photocatalyst reduced aryl halides under visible‐light irradiation in polar organic solvent and in water.The present study provides a promising strategy to realize two‐photon activity of PDI in common solvents for photocatalytic applications.展开更多
Recently, perylene diimide （PDI） derivatives were attractive as the electron-deficient acceptor materials in non-fullerene organic solar cells since Tang first used a single PDI compound as the n-type semiconductor ...Recently, perylene diimide （PDI） derivatives were attractive as the electron-deficient acceptor materials in non-fullerene organic solar cells since Tang first used a single PDI compound as the n-type semiconductor to fabricate photovoltaic devices in 1986, which achieved a power conversion efficiency of 1%. Beside the monomeric PDIs, the linear and three dimensional （3D） PDl-based small molecular acceptors have also made great achievements with the power conversion efficiencies over 9.0% in single- junction polymer solar cells, and over 10.0% in tandem solar cells. The excellent device performance can be realized by forming suitable twisted structure, developing suitable donor materials and optimizing device technologies. In this review, we summarize the recent development of PDl-based small molecular non-fullerene acceptors in non-fullerene organic solar cells, including molecular design strategies and structure-property relationships.展开更多
N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A...N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.展开更多
Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two...Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.展开更多
Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI...Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI）. Cationic PFP, single-stranded nucleic acid and PDI were used as signal reporter, probe and fluorescence quencher, respectively. In the presence of nucleic acids, they form complexes with PFP and PDI through strong electrostatic attraction interactions, resulting in PDI aggregating on nucleic acids and fluorescence of PFP being quenched. When nucleic acids are hydrolyzed by enzymes or their conformation is changed via recognizing targets, the effective aggregation of PDI is disrupted and the quenching ability is decreased. Thus the fluorescence of PFP recovers significantly. By taking advantage of the mechanism, we construct a new biosensor for endonuclease and small molecules detection. Here, S1 nuclease and bisphenol A are used as model systems. The detection limit of the SI nuclease and BPA are1.0×10^-6U/mL and 0.05 ng/mL, respectively. Our method is sensitive, cost-effective and simple, and provides a new platform for bioanalysis.展开更多
In recent years, a large library of n-type polymers have been developed and widely used as acceptor materi- als to replace fullerene derivatives in polymer solar cells （PSCs）, stimulating the rapid expansion of rese...In recent years, a large library of n-type polymers have been developed and widely used as acceptor materi- als to replace fullerene derivatives in polymer solar cells （PSCs）, stimulating the rapid expansion of research on so-called all-polymer solar cells （aPSCs）. In particular, rylene diimide-based n-type polymer acceptors have attracted broad research interest due to their high electron mobility, suitable energy levels, and strong light-harvesting ability in the visible region. Among various polymer acceptors, rylene diimide-based poly- mers presented best performances when served as the acceptor materials in aPSCs. Typically, a record power conversion efficiency （PCE） of 7.7% was very recently achieved from an aPSC with a rylene diimide polymer derivative as the acceptor component. In this review, we highlight recent progress of n-type polymers orig- inated from two significant classes of rylene diimide units, namely naphthalene diimide （NDI） and perylene diimide （PDI）, as well as their derivatives for aPSC applications.展开更多
Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for co...Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.展开更多
A series of core-expanded naphthalene diimides（NDI-DTYM） and thiophene-based derivatives（1a-c）were designed and synthesized to investigate the relationship between molecular structures and the highest occupied mol...A series of core-expanded naphthalene diimides（NDI-DTYM） and thiophene-based derivatives（1a-c）were designed and synthesized to investigate the relationship between molecular structures and the highest occupied molecular orbital（HOMO） energy levels but has little impact on the lowest unoccupied molecular orbital（LUMO） energy levels.The results demonstrated that increasing the number of thiophene units can gradually elevate the HOMO energy levels but had little impact on the LUMO energy levels.The n-channel organic field-effect transistors（OFETs） based on 1b and 1c have demonstrated that these almost unchanged LUMO energy levels are proper to transport electrons.展开更多
文摘Doping perylene diimide(PDI)into a polymer matrix is a simple strategy to prepare near-infrared(NIR)reflective materials,but the mechanical properties and NIR reflectance properties are significantly compromised due to macro-phase separation.In this study,a novel polymer(denoted as PU-PDI)with intrinsic NIR reflective proper⁃ties was synthesized by covalent incorporation of PDI units into polyurethane chains.Its photophysical characteris⁃tics,mechanical property and NIR reflectance property are investigated in detail.The results show that covalent in⁃corporation reduces the severe aggregation of PDI units,thereby endows PU-PDI with excellent mechanical property.The elongation at break of PU-PDI can reach more than 700%,and the breaking strength is 34.11 MPa.Moreover,compared to the blending system,PU-PDI possesses enhanced NIR reflection ability due to the better dispersion of PDI units.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231270)the National Science Fund for Distinguished Young Scholars(22125804).
文摘Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using linear-shaped ligands have not yet been explored.Herein,we present the design of NUT-123 by incorporating a near-linear perylene diimide(PDI)derivate,PDI-CH_(3)-COOH,into the preselected zirconium-based MOLs.3D electron diffraction confirms the successful construction of a novel topology in NUT-123.Furthermore,the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI-CH_(3)-COOH.NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility,achieving 100%conversion of various organic sulfides.Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer.This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
基金supported by Open Foundation of Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(Grant No.JDSX2023008)Joint Fund of Scientific and Technological Research and Development Program of Henan Province(222301420009)the funding of Zhengzhou University.
文摘Organic electrodes are considered competitive candidates for the next-generation high-performance energy storage devices owing to their advantages of structural flexibility and abundant resources.However,solubility and low electronic conductivity have been major obstacles to the practical application.To address these challenges,the structural design and interfacial regulation of organic electrodes are crucial to the performance enhancement.Herein,we report on aπ-conjugated polymer cathode material of poly(3,4,9,10-perylenetetracarboxylic diimide)(PPI)for metal ion batteries,and the performance optimization is achieved by matching suitable conductive carbons and liquid electrolytes.Ultimately,the carbon nanotubes(CNTs)with weight content of 25%and 1 M NaPF6 in ethylene carbonate/diethyl carbonate electrolyte are introduced to assemble the batteries,and the discharge specific capacity,cycling stability and rate performance are enhanced effectively.The PPI-CNTjjNa battery displays high specific capacities of 146.4 and 117 mAh g^(-1) at current densities of 0.1 C and 5 C,respectively.Furthermore,PPI-CNTjjNa battery demonstrates excellent long-term cycling stability of 5000 cycles with low 0.007 mAh g^(-1)capacity decay per cycle at 1C due to the thin and uniform cathode electrolyte interphase.Moreover,the PPI-CNTjjNa battery presents good cycling stability at high temperatures of 60℃,and retains a capacity of 132.5 mAh g^(-1) after 300 cycles with a high capacity retention rate of 96.9%.Besides,PPI-CNT displays good electrochemical performance and compatibility in lithium-ion and potassium-ion batteries.This work provides an alternative optimization strategy for organic electrodes applied in long-lifetime metal ion batteries.
基金Yunfu 2023 Innovation Team Project,China(CYRC202305)。
文摘Mechanochromic materials respond to external stimuli and provide early warnings of material damage.Perylene diimide(PDI)-based materials have attracted attention because of their outstanding fluorescence performance.However,the application of PDI in mechanochromism is limited by the difficulty for mechanical forces to disrupt the aggregation of PDI and its derivatives,as well as the fluorescence quenching caused by continuousπ-πstacking between PDI molecules.To eliminate the fluorescence quenching effect caused by the aggregation of PDI and broaden its application fields,polyhedral oligomeric silsesquioxane(POSS)-PDI-POSS(PPP)was screened as PDI doping.The photophysical properties of PPP in both monomeric and aggregated states in different solvents were studied.Then,PPP and styrene-butadiene-styrene block copolymer(SBS)were mixed to prepare the PPP/SBS film.The mechanochromic properties of PPP/SBS film were explored.The fluorescence emission spectra confirmed that when the PPP mass fraction increased to 0.30%,the PPP/SBS film exhibited mechanochromic behavior under uniaxial deformation due to the changes in the molecular packing.
基金supported by the Beijing Natural Science Foundation(Nos.2242004 and 2232027)the National Natural Science Foundation of China(No.22171021)the China Postdoctoral Science Foundation(No.2023M730245).
文摘Radical anions of electron-deficient perylene diimides(PDI)are attractive near-infrared(NIR)absorbers for photothermal conversion;however,their stability is often compromised by strong aggregation and reoxidation in air.Herein,we present a class of bacterial composites hybridized with a newly synthesized doubly-strapped PDI cyclophane,termed“Gemini Box”(GBox-3^(4+)),which features air-stable PDI radicals for NIR photothermal conversion.The effective spatial isolation provided by the double-sided cationic molecular straps allows GBox-3^(4+)to completely suppress chromophore aggregation,even in concentrated aqueous solutions up to 2 mmol/L,thereby preserving its characteristic fluorescence for live-cell imaging.After incubation of bacteria with GBox-3^(4+),the radical species PDI·-have been found to stably exist in the bacterial composites under ambient conditions,both in aqueous suspension and solid forms.Further experiments demonstrate that the air stability of the radical species relies on the simultaneous presence of the doubly-strapped PDI dye and the bacteria.Moreover,the dye-bacterial composites exhibited an high-efficiency NIR photothermal effect with high durability,enabling their application as photothermal agents for seawater desalination.This work provides a new access to the in situ fabrication of photothermal materials from biomass,relying on the rational molecular design and the unique microenvironment of bacteria.
基金support from the National Natural Science Foundation of China(Nos.22071007,22020102001,22335002)the National Key R&D Program of China(No.2022YFB3602802)+3 种基金Beijing Natural Science Foundation(No.Z220025)the National Facility for Protein Science in Shanghai,Shanghai Advanced Research Institute,CAS,for providing technical support in X-ray diffraction data collectionthe High-Performance Computing Platform of Peking University for supporting the computational workthe support of BMS Junior Fellow program。
文摘Regioselevtive functionalization of perylene diimides(PDIs)at bay area often requires multistep synthesis and strenuous recrystallization.Direct bromination of perylene diimides only afford the 1,6 and 1,7-regioisomers.More importantly,the 1,6-dibromo regioisomers could only be separated by preparative HPLC.Herein,we report a promising strategy for constructing Janus backbone of BN-doped perylene diimide derivatives.This Janus-type configuration results in the unique regioselective functionalization of BN-JPDIs,which yields exclusively the 1,6-regioisomers.Further investigation shows that the Janus-type configuration leads to a net dipole moment of 1.94 D and intramolecular charge transfer,which causes substantial changes on the optoelectronic properties.Moreover,the single crystal organic field-effect transistors based on BN-JPDIs exhibit electron mobilities up to 0.57 cm^(2)V^(-1)s^(-1),showcasing their potential as versatile building block towards high-performance n-type organic semiconductors.
基金supported by the National Research Foundation(NRF)of Korea(Nos.2023R1A2C3007715,2021R1A4A1032515,RS-2023-00281944)funded by the Ministry of Science and ICT(MSIT)of Korea+1 种基金Korea Toray Science Foundation,Shaanxi Fundamental Science Research Project for Chemistry&Biology(No.22JHQ035)Natural Science Basic Research Program of Shaanxi Province(No.2024JC-YBMS-081)。
文摘Compared to organic thin films,organic single crystals offer significant potential in organic phototransistors(OPTs)due to their enhanced charge transport,large surface area,and defect-free nature.However,the development of n-type semiconductors has lagged behind p-type semiconductors.To enhance semiconductor device performance,a doping process can be employed,which typically involves the introduction of charged impurities into the crystalline semiconducting material.Its aim is to reduce the Ohmic losses,increase carrier density,improve transport capabilities,and facilitate effective carrier injection,ultimately enhancing the electrical properties of the material.Traditional doping processes,however,often pose a risk of damaging the structure of single crystals.In this study,we have synthesized novel cyanosubstituted chiral perylene diimides,which self-assemble into two-dimensional single crystals that can be used for n-type semiconductor devices.We have employed a surface doping strategy using diethylamine vapor without disrupting the crystal structure.The fabricated devices exhibit significantly higher charge transport properties after doping,achieving a maximum electron mobility of 0.14 cm^(2)V^(-1)s^(-1),representing an improvement of over threefold.Furthermore,the optoelectronic performance of the doped devices has significantly improved,with the external quantum efficiency increased by over 9 times and the significantly improved response time.These results suggest that our surface doping technology is a promising way for enhancing the performance of 2D organic single-crystal OPTs.
基金supported by the National Natural Science Foundation of China(Nos.21406027,21875027,and 22174009)the Medical and Engineering Joint Project of Natural Science Foundation of Liaoning Province(No.2021-YGJC-17)Supercomputing Center of Dalian University of Technology。
文摘The first example of metal Sn-fused perylene diimides(PDI)derivative(Sn-PDI)was designed,synthesized,and investigated.To obtain this type compound,a simple one-pot synthesis,named stannylative cycloaddition reaction,has been successfully developed via a palladium-based catalyst system.The novel mechanism exhibits that the reaction experiences oxidative addition,Pd-cyclization,stannylation,Pd-Sn-cyclization,and reductive elimination processes successively.This stannylative cycloaddition does realize uniqueσ-πhyperconjugation effect and therefore significantly influencing on the photophysical,electrochemical and excited state properties.Compared with those of PDI,both of the absorption and fluorescence spectra of Sn-PDI display large red-shifts over 20 nm.The electron energy levels of Sn-PDI have changed with an uncommon regulation.And Sn-PDI gives a considerably raised highest occupied molecular orbital(HOMO)level of-6.00 eV More importantly,the singlet excitons of Sn-PDI could efficiently intersystem cross(ISC)into triplet state with a long lifetime of 17.8μs,which is far longer than that(4.4 ns)of PDI.
基金financially supported by 973 Program(No.2013CB834702)the National Natural Science Foundation of China(No.91433114)
文摘Two polymers containing （E）-2,3-bis（thiophen-2-yl）acrylonitrile （CNTVT） as a donor unit, perylene diimide （PDI） or naphthalene diimide （NDI） as an acceptor unit, are synthesized by the Stille coupling copolymerization, and used as the electron acceptors in the solution-processed organic solar cells （OSCs）. Both polymers exhibit broad absorption in the region of 300-850 nm. The LUMO energy levels of the resulted polymers are ca. -3.93 eV and the HOMO energy levels are -5.97 and -5.83 eV. In the binary blend OSCs with PTB7-Th as a donor, PDI polymer yields the power conversion efficiency （PCE） of up to 1.74%, while NDI polymer yields PCE of up to 3.80%.
基金the National Natural Science Foundation of China(No.21972052).
文摘As an emerging organic semiconductor,perylene diimide(PDI)self-assembly has attracted tremendous attention in the aspects of solar cells,sensors,fluorescence probes and n-transistors,etc.In term of photocatalysis,various photocatalysts based on PDI self-assembly exhibit some unique properties,such as intrinsicΠ-Πstacking structure,fast internal charge transfer,band-like electronic structure,flexible structural modifiability,well-defined morphological adjustability and excellent light absorption.This paper mainly presents recent progress on PDI self-assembly regarding how to regulate the electronic structure of PDI self-assembly.In addition,the photocatalytic applications of PDI self-assembly and its complexes were reviewed,such as environmental remedy,energy productions,organic synthesis and photodynamic/photothermal therapy,further highlighting related photocatalytic mechanisms.Finally,the review contents and some perspectives on photocatalytic research of PDI selfassembly were summarized,and some key scientific problems were put forward to direct related photocatalytic research in future.
基金financially supported by the Ministry of Science and Technology of China (No. 2014CB643501)the National Natural Science Foundation of China (Nos. 21634004 and 51403070)+1 种基金the Foundation of Guangzhou Science and Technology Project (No. 201707020019)Zhi-Cheng Hu thanks the financial support from China Postdoctoral Science Foundation (No. 2017M622684)
文摘We present here a series of perylene diimide(PDI)based isomeric conjugated polymers for the application as efficient electron acceptors in all-polymer solar cells(all-PSCs).By copolymerizing PDI monomers with 1,4-diethynylbenzene(para-linkage)and 1,3-diethynylbenzene(meta-linkage),isomeric PDI based conjugated polymers with parallel and non-parallel PDI units inside backbones were obtained.It was found that para-linked conjugated polymer(PA)showed better solubility,strongerπ-πstacking,more favorable blend morphology,and better photovoltaic performance than those of meta-linked conjugated polymers(PM)did.Device based on PTB7-Th:PA(PTB7-Th:poly{4,8-bis[5-(2-ethylhexyl)-thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophene-4,6-diyl})showed significantly enhanced photovoltaic performance than that of PTB7-Th:MA(3.29%versus 0.92%).Moreover,the photovoltaic performance of these polymeric acceptors could be further improved via a terpolymeric strategy.By copolymerizing a small amount of meta-linkages into PA,the optimized terpolymeric acceptors enabled to enhance photovoltaic performance with improved the short-circuit current density(Jsc)and fill factor(FF),resulting in an improved power conversion efficiency(PCE)of 4.03%.
文摘The recyclable and stable ZnFe_(2)O_(4) small particle decorated one‐dimensional perylene diimide(PDI)S‐scheme heterojunction(1D PDI/ZnFe_(2)O_(4))is prepared by the hydrochloric acid‐mediated(HCl‐mediated)strategy,interestingly,the morphology of the 1D PDI/ZnFe_(2)O_(4) can also be effectively regulated by HCl‐mediated process,the existence of HCl can regulate PDI into a uniform rod structure,while the co‐existence of HCl and PDI can limit ZnFe_(2)O_(4) to become the uniform small particles.More importantly,based on the 1D rod structure of PDI and the small size effect of ZnFe_(2)O_(4),carriers can migrate to the surface more easily,which can improve the photocatalytic activity.Meanwhile,due to the appropriate energy level structure,the S‐scheme heterojunction structure is formed between PDI and ZnFe_(2)O_(4),which eliminates meaningless photo‐generated charge carriers through recombination and introduces strong redox to further enhance the photodegradation effect,thereby,1D PDI/ZnFe_(2)O_(4) exhibits excellent photocatalytic ability,under the visible light irradiation,the degradation rate of tetracycline(TC)with 1D PDI/ZnFe_(2)O_(4)(66.67%)is 9.18 times that with PDI(7.26%)and 9.73 times that with ZnFe_(2)O_(4)(6.85%).This work proposes new ideas for the assembly of magnetic organic‐inorganic S‐scheme heterojunction photocatalysts.
基金supported by the National Natural Science Foundation of China(21525729,21590811,21521062,2177168)the "Strategic Priority Research Program" of the Chinese Academy of Sciences(XDA09030200)the "CAS Interdisciplinary Innovation Team Program"~~
文摘The consecutive two‐photon photocatalytic behavior of perylene diimide(PDI)enables it to catalyze photoreduction reactions that are thermodynamically unfavorable via single‐photon processes.In this work,we developed a heterogeneous PDI photocatalyst by covalently binding PDI molecules on the surface of nanosilica.This photocatalyst structure overcomes the intrinsic limitation of the low solubility of PDI,but retains its consecutive two‐photon photocatalytic property.Detailed characterization of the photocatalyst by techniques such as thermogravimetric analysis,solid‐state nuclear magnetic resonance spectroscopy,and Fourier transform infrared spectroscopy indicated that the PDI molecules were anchored covalently on the surface of nanosilica.The obtained photocatalyst reduced aryl halides under visible‐light irradiation in polar organic solvent and in water.The present study provides a promising strategy to realize two‐photon activity of PDI in common solvents for photocatalytic applications.
基金supported by the National Science Foundation of China (NSFC, Nos. 51573107, 91633301 and 21432005)the Foundation of State Key Laboratory of Polymer Materials Engineering (No. sklpme 2017-2-04)
文摘Recently, perylene diimide （PDI） derivatives were attractive as the electron-deficient acceptor materials in non-fullerene organic solar cells since Tang first used a single PDI compound as the n-type semiconductor to fabricate photovoltaic devices in 1986, which achieved a power conversion efficiency of 1%. Beside the monomeric PDIs, the linear and three dimensional （3D） PDl-based small molecular acceptors have also made great achievements with the power conversion efficiencies over 9.0% in single- junction polymer solar cells, and over 10.0% in tandem solar cells. The excellent device performance can be realized by forming suitable twisted structure, developing suitable donor materials and optimizing device technologies. In this review, we summarize the recent development of PDl-based small molecular non-fullerene acceptors in non-fullerene organic solar cells, including molecular design strategies and structure-property relationships.
基金Shanghai Natural Science Foundation,China(No.13ZR1400700)The Program for Innovative Research Team in University,China(No.IRT1221)
文摘N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.
基金National Natural Science Foundation of China(Nos.92161111,21901037 and 21901038)。
文摘Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.
基金the financial support from the National Natural Science Foundation of China(No. 21675106)the 111 Project(No. B14041)+2 种基金Natural Science Basic Research Plan in Shaanxi Province of China (No. 2017JM2019)the Program for Changjiang Scholars and Innovative Research Team in University (No. 14R33)the Program for Innovative Research Team in Shaanxi Province(No. 2014KCT-28)
文摘Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI）. Cationic PFP, single-stranded nucleic acid and PDI were used as signal reporter, probe and fluorescence quencher, respectively. In the presence of nucleic acids, they form complexes with PFP and PDI through strong electrostatic attraction interactions, resulting in PDI aggregating on nucleic acids and fluorescence of PFP being quenched. When nucleic acids are hydrolyzed by enzymes or their conformation is changed via recognizing targets, the effective aggregation of PDI is disrupted and the quenching ability is decreased. Thus the fluorescence of PFP recovers significantly. By taking advantage of the mechanism, we construct a new biosensor for endonuclease and small molecules detection. Here, S1 nuclease and bisphenol A are used as model systems. The detection limit of the SI nuclease and BPA are1.0×10^-6U/mL and 0.05 ng/mL, respectively. Our method is sensitive, cost-effective and simple, and provides a new platform for bioanalysis.
基金financial support by the "Thousand Talents Program for Young Scholars" of China
文摘In recent years, a large library of n-type polymers have been developed and widely used as acceptor materi- als to replace fullerene derivatives in polymer solar cells （PSCs）, stimulating the rapid expansion of research on so-called all-polymer solar cells （aPSCs）. In particular, rylene diimide-based n-type polymer acceptors have attracted broad research interest due to their high electron mobility, suitable energy levels, and strong light-harvesting ability in the visible region. Among various polymer acceptors, rylene diimide-based poly- mers presented best performances when served as the acceptor materials in aPSCs. Typically, a record power conversion efficiency （PCE） of 7.7% was very recently achieved from an aPSC with a rylene diimide polymer derivative as the acceptor component. In this review, we highlight recent progress of n-type polymers orig- inated from two significant classes of rylene diimide units, namely naphthalene diimide （NDI） and perylene diimide （PDI）, as well as their derivatives for aPSC applications.
基金supported by the National Natural Science Foundation of China (No. 22171219)the Fundamental Research Funds for the Central Universities (No. xzy022021004)。
文摘Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.
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A series of core-expanded naphthalene diimides（NDI-DTYM） and thiophene-based derivatives（1a-c）were designed and synthesized to investigate the relationship between molecular structures and the highest occupied molecular orbital（HOMO） energy levels but has little impact on the lowest unoccupied molecular orbital（LUMO） energy levels.The results demonstrated that increasing the number of thiophene units can gradually elevate the HOMO energy levels but had little impact on the LUMO energy levels.The n-channel organic field-effect transistors（OFETs） based on 1b and 1c have demonstrated that these almost unchanged LUMO energy levels are proper to transport electrons.
