Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O soluti...Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O solution.The assembly and fluorescence behavior of PDI-COOH/Ca^(2+)were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca^(2+),we proposed the fluorescence emission mechanism of PDI-COOH/Ca^(2+)in THF/H_(2)O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.展开更多
Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Her...Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.展开更多
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
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
The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their p...The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their photocatalytic performance.To achieve closeπ-πstacking,the suitable design of molecular structure is essential.Therefore,two isomers of pyridine carboxylic acid-modified perylene monoimide(PMI)were designed and synthesized,namely PM5A and PM6A.In aqueous solution,these molecules self-assemble into aggregates,which exhibit distinct stacking properties and optical characteristics.Upon photoexcitation,the looseπ-πstacking of PM5A favors the generation of charge-transfer excitons(CTEs)over charge-separation excitons(CSEs).In contrast,PM6A,stabilized by intermolecular hydrogen bonds and possessing closeπ-πstacking,undergoes efficient charge separation(CS)to produce CSEs within 4.5 picoseconds.When incorporated into metal-insulatorsemiconductor(MIS)photosystems with polyvinylpyrrolidone(PVP)-capped Pt,the Pt/PVP/PM6A system demonstrates a hydrogen evolution rate(HER)of 8100μmol g^(-1)h^(-1),nearly five times higher than that of the Pt/PVP/PM5A system.Additionally,the maximum apparent quantum efficiency(AQE)reaches approximately 2.1%under irradiation with light of a single wavelength of λ=425 nm.展开更多
The major challenge in photocatalytic water splitting lies in water oxidation reactions,which still suffer from poor charge separation.This study overcame inefficient charge separation by establishing a robust interfa...The major challenge in photocatalytic water splitting lies in water oxidation reactions,which still suffer from poor charge separation.This study overcame inefficient charge separation by establishing a robust interfacial electric field through the electrostatic-driven assembly of Co_(3)O_(4) nanoparticles with a perylene imide supramolecule(PDINH).The well-aligned band structures and intimate interfacial contact in the PDINH/Co_(3)O_(4) heterostructure create an enhanced interfacial electric field that is 4.1-and 53.2-fold stronger than those of individual PDINH and Co_(3)O_(4),thus promoting directional charge separation and transfer.Moreover,S-scheme charge transfer strongly preserves the oxidative holes in PDINH to drive efficient water oxidation reactions.Consequently,PDINH/Co_(3)O_(4) composite achieves a photocatalytic oxygen evolution rate of 29.26 mmol g^(–1) h^(–1) under visible light irradiation,8.2-fold improvement over pristine PDINH,with an apparent quantum yield of 6.66%at 420 nm.This study provides fundamental insights into interfacial electric field control for the development of high-performance organic photocatalysts for efficient water oxidation.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
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
In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylen...In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.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
In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduce...In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer(PET)effect.Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized,and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry(HRMS),nuclear magnetic resonance hydrogen and carbon spectroscopy(~1H and~(13)C NMR).The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration.The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process.Despite the similarities in chemical structures,the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine.In the direct irradiation experiments of ionizing radiation,the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4,respectively.Furthermore,density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 e V and 1.13 e V,respectively.A wider energy range has a stronger driving force on electrons,which is conducive to fluorescence quenching.Both femtosecond transient absorption spectroscopy(fs-TAS)and transient fluorescence spectroscopy(TFS)tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant.Although both isomers can significantly reduce LOD during PET process,PDI-B with aromatic amine has a wider detection range of 0.118—240 Gy due to its larger emission enhancement,which is a leap of three orders of magnitude.It breaks through the detection range of gamma radiation reported in existing studies,and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.展开更多
In semiconductor photocatalysts,the easy recombination of photogenerated carriers seriously affects the application of photocatalytic materials in water treatment.To solve the serious problem of electron−hole pair rec...In semiconductor photocatalysts,the easy recombination of photogenerated carriers seriously affects the application of photocatalytic materials in water treatment.To solve the serious problem of electron−hole pair recombination in perylene diimide(PDI)organic semiconductors,we loaded ferric hydroxyl oxide(FeOOH)on PDI materials,successfully prepared novel FeOOH@PDI photocatalytic materials,and constructed a photo-Fenton system.The system was able to achieve highly efficient degradation of BPA under visible light,with a degradation rate of 0.112 min^(−1)that was 20 times higher than the PDI system,and it also showed universal degradation performances for a variety of emerging organic pollutants and anti-interference ability.The mechanism research revealed that the FeOOH has the electron trapping property,which can capture the photogenerated electrons on the surface of PDI,effectively reducing the compounding rate of photogenerated carriers of PDI and accelerating the iron cycling and H2O2 activation on the surface of FeOOH at the same time.This work provides new insights and methods for solving the problem of easy recombination of carriers in semiconductor photocatalysts and degrading emerging organic pollutants.展开更多
A series of N, N′ dialkyl (and aryl) perylene 3,4:9, 10 bis (dicarboximide) compounds were prepared and purified, and their photoelectric properties as organic photoconductors were explored. It is found that N, N′...A series of N, N′ dialkyl (and aryl) perylene 3,4:9, 10 bis (dicarboximide) compounds were prepared and purified, and their photoelectric properties as organic photoconductors were explored. It is found that N, N′ dimethyl perylene 3,4:9, 10 bis (dicarboximide) and perylene 3,4:9,10 tetracarboxylic acid bisbenzimidazole show excellent photoconductivities, their charge acceptance reaches 700 V and 485 V, and the photosensitivity is 45 lx·s and 10 lx·s with dark decays 70 and 60 V/s respectively. The introduction of chlorine atoms can improve their photoelectric properties. SEM analyses also show that the dispersion of pigment in OPC could affect its photosensitivity.展开更多
The matched energy band structure and efficient carrier separation efficiency are the keys to heterogeneous photocatalytic reactions.A novel organic/inorganic step scheme(S-scheme)heterojunction PDI-Urea/BiOBr composi...The matched energy band structure and efficient carrier separation efficiency are the keys to heterogeneous photocatalytic reactions.A novel organic/inorganic step scheme(S-scheme)heterojunction PDI-Urea/BiOBr composite photocatalyst was constructed by simple solvothermal reaction combined with in-situ growth strategy.The composite photocatalyst not only has high chemical stability,but also can generate and accumulate a large number of active species(h^(+),·O_(2)^(-),·OH,H_(2)O_(2)).PDI-Urea/BiOBr showed higher photocatalytic activity for the degradation of antibiotic such as ofloxacin(OFLO),tetracycline(TC)and the production of H_(2)O_(2) in the spectral range of 400-800 nm.The apparent rate constant of 15%PDI-Urea/BiOBr for photocatalytic degradation of TC(or OFLO)was 2.7(or 2.5)times that of pure BiOBr and 1.7(or 1.8)times that of pure PDI-Urea.The H_(2)O_(2) evolution rate of 15%PDI-Urea/BiOBr was 2.5 times that of PDI-Urea and 1.5 times that of BiOBr,respectively.This work has formed a mature S-scheme heterojunction design thought and method,which offers new visions for the development of heterogeneous photocatalysts.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
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
An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoet...An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoethyl）-piperazine. Then imidization of perylene-3, 4, 9, 10-tetracarboxylic acid dianhydride with 2,4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was carried out to afford a novel perylene derivative bearing two melamine blocks （S2） and 1, 6, 7, 12-tetra（4-tert-butyl phenoxy）-perylene-3, 4, 9, 10-tetracarboxylic acid bisimide （S1. The hydrogen-bonding interactions between S1 and S2 were investigated by IH NMR spectrum, UV/Vis spectrum and fluorescence spectrum. The influences on the morphologies of S1·S2 aggregates were investigated. The results show that well-defined nanofibers with a diameter of about 100 nm can be obtained by self-assembly between S1 and S2 only in CH2Cl2 solution. Based on these results, guidelines for the molecular design and self-assembly of supramolecular polymer materials are presented.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
文摘Bay-site carboxyl functionalized perylene diimide derivative 1,7-COOH-PDI-C_(12)(PDI-COOH)was synthesized and distinct enhanced fluorescence was observed through combining with calcium ion(Ca^(2+))in THF/H_(2)O solution.The assembly and fluorescence behavior of PDI-COOH/Ca^(2+)were studied in detail by changing hydration state with different concentrations.Based on the differences in assembly morphology and stoichiometric ratios of PDICOOH/Ca^(2+),we proposed the fluorescence emission mechanism of PDI-COOH/Ca^(2+)in THF/H_(2)O and THF,respectively.This work reveals a novel strategy of aggregated state fluorescence enhancement and reminds us of the important role of water in molecular fluorescence emission and assembly.
基金supported by National Natural Science Foundation of China(No.523B2070,No.52225606).
文摘Polymeric perylene diimide(PDI)has been evidenced as a good candidate for photocatalytic water oxidation,yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration.Herein,with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern,the electronic structure is theoretically illustrated by the first-principles density functional theory calculations,suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI.It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal orbital Hamiltonian group analysis.The calculations of reaction free energy changes indicate that the oxygen evolution reaction should follow the reaction pathway of H_(2)O→^(*)OH→^(*)O→^(*)OOH→^(*)O_(2)with an overpotential of 0.81 V.Through an in-depth theoretical computational analysis in the atomic and electronic structures,the origin of photocatalytic oxygen evolution activity for PDI is well illustrated,which would help the rational design and modification of polymeric photocatalysts for efficient oxygen evolution.
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 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supported from the NSFC(Nos.22302038 and 22406027).
文摘The tightness of π-π stacking in supramolecular organic semiconductors plays a crucial role in governing the spatial separation and migration dynamics of photogenerated charge carriers,ultimately determining their photocatalytic performance.To achieve closeπ-πstacking,the suitable design of molecular structure is essential.Therefore,two isomers of pyridine carboxylic acid-modified perylene monoimide(PMI)were designed and synthesized,namely PM5A and PM6A.In aqueous solution,these molecules self-assemble into aggregates,which exhibit distinct stacking properties and optical characteristics.Upon photoexcitation,the looseπ-πstacking of PM5A favors the generation of charge-transfer excitons(CTEs)over charge-separation excitons(CSEs).In contrast,PM6A,stabilized by intermolecular hydrogen bonds and possessing closeπ-πstacking,undergoes efficient charge separation(CS)to produce CSEs within 4.5 picoseconds.When incorporated into metal-insulatorsemiconductor(MIS)photosystems with polyvinylpyrrolidone(PVP)-capped Pt,the Pt/PVP/PM6A system demonstrates a hydrogen evolution rate(HER)of 8100μmol g^(-1)h^(-1),nearly five times higher than that of the Pt/PVP/PM5A system.Additionally,the maximum apparent quantum efficiency(AQE)reaches approximately 2.1%under irradiation with light of a single wavelength of λ=425 nm.
文摘The major challenge in photocatalytic water splitting lies in water oxidation reactions,which still suffer from poor charge separation.This study overcame inefficient charge separation by establishing a robust interfacial electric field through the electrostatic-driven assembly of Co_(3)O_(4) nanoparticles with a perylene imide supramolecule(PDINH).The well-aligned band structures and intimate interfacial contact in the PDINH/Co_(3)O_(4) heterostructure create an enhanced interfacial electric field that is 4.1-and 53.2-fold stronger than those of individual PDINH and Co_(3)O_(4),thus promoting directional charge separation and transfer.Moreover,S-scheme charge transfer strongly preserves the oxidative holes in PDINH to drive efficient water oxidation reactions.Consequently,PDINH/Co_(3)O_(4) composite achieves a photocatalytic oxygen evolution rate of 29.26 mmol g^(–1) h^(–1) under visible light irradiation,8.2-fold improvement over pristine PDINH,with an apparent quantum yield of 6.66%at 420 nm.This study provides fundamental insights into interfacial electric field control for the development of high-performance organic photocatalysts for efficient water oxidation.
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 Research Project for Outstanding Young People in Universities of Anhui Province(No.2023AH030099)the China Postdoctoral Science Foundation(No.2023M733378)+3 种基金the National Natural Science Foundation of China(No.21702042,No.22305059,No.22103010)the National University Students'Innovation and Entrepreneurship Training Program(No.202311059024)the Anhui Provincial Natural Science Foundation(No.2308085QB59)the Anhui Provincial Excellent Scientific Research and Innovation Team(No.2022AH010096).
文摘In this study,diodo boron dipyrromethene(BODIPY)is employed a8 the energy donor and 3,4,9,10-perylene tetracarboxylic dianhydride(PDA)as the energy acceptor,enabling the synthesis of two new compounds:a BODIPY-perylene dyad named P1,and a triad named P2.To investigate the impact of the energy donor on the photophysical processes of the system,P1 comprises one diodo-BODIPY unit and one PDA unit,whereas P2 contains two diodo-BODIPY moieties and one PDA unit.Due to the good spectral complementarity between diiodo-BODIPY and PDA,these two compounds exhibit excellent light-harvesting capabilities in the 400-620 nm range.Steady-state fluorescence spectra demonstrate that when preferentially exciting the diodo-BODIPY moiety,it can effectively transfer energy to PDA;when selectively exciting the PDA moiety,quenching of PDA fluorescence is observed in both P1 and P2.Nanosecond transient absorption results show that both compounds can efficiently generate triplet excited states,which are located on the PDA part.The lifetimes of the triplet states for these two compounds are 103 and 89μs,respectively,significantly longer than that of diiodo-BODIPY.The results from the photooxidation experiments reveal that both P1 and P2 demonstrate good photostability and photooxidation capabilities,with P2 showing superior photooxidative efficiency.The photooxidation rate constant for P2 is 1.3 times that of P1,and its singlet oxygen quantum yield is 1.6 times that of P1.The results obtained here offer valuable insights for designing new photosensitizers.
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financial support from the National Natural Science Foundation of China(Grant No.21801016)the Science and Technology on Applied Physical Chemistry Laboratory(Grant No.6142602220304)。
文摘In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer(PET)effect.Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized,and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry(HRMS),nuclear magnetic resonance hydrogen and carbon spectroscopy(~1H and~(13)C NMR).The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration.The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process.Despite the similarities in chemical structures,the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine.In the direct irradiation experiments of ionizing radiation,the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4,respectively.Furthermore,density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 e V and 1.13 e V,respectively.A wider energy range has a stronger driving force on electrons,which is conducive to fluorescence quenching.Both femtosecond transient absorption spectroscopy(fs-TAS)and transient fluorescence spectroscopy(TFS)tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant.Although both isomers can significantly reduce LOD during PET process,PDI-B with aromatic amine has a wider detection range of 0.118—240 Gy due to its larger emission enhancement,which is a leap of three orders of magnitude.It breaks through the detection range of gamma radiation reported in existing studies,and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.
基金supported by the National Natural Science Foundation of China(No.22306178 and 22176155)Outstanding Youth Talents of Sichuan Science and Technology Program(No.22JCQN0061)+1 种基金National Natural Science Foundation of China(No.22306012)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110578).
文摘In semiconductor photocatalysts,the easy recombination of photogenerated carriers seriously affects the application of photocatalytic materials in water treatment.To solve the serious problem of electron−hole pair recombination in perylene diimide(PDI)organic semiconductors,we loaded ferric hydroxyl oxide(FeOOH)on PDI materials,successfully prepared novel FeOOH@PDI photocatalytic materials,and constructed a photo-Fenton system.The system was able to achieve highly efficient degradation of BPA under visible light,with a degradation rate of 0.112 min^(−1)that was 20 times higher than the PDI system,and it also showed universal degradation performances for a variety of emerging organic pollutants and anti-interference ability.The mechanism research revealed that the FeOOH has the electron trapping property,which can capture the photogenerated electrons on the surface of PDI,effectively reducing the compounding rate of photogenerated carriers of PDI and accelerating the iron cycling and H2O2 activation on the surface of FeOOH at the same time.This work provides new insights and methods for solving the problem of easy recombination of carriers in semiconductor photocatalysts and degrading emerging organic pollutants.
文摘A series of N, N′ dialkyl (and aryl) perylene 3,4:9, 10 bis (dicarboximide) compounds were prepared and purified, and their photoelectric properties as organic photoconductors were explored. It is found that N, N′ dimethyl perylene 3,4:9, 10 bis (dicarboximide) and perylene 3,4:9,10 tetracarboxylic acid bisbenzimidazole show excellent photoconductivities, their charge acceptance reaches 700 V and 485 V, and the photosensitivity is 45 lx·s and 10 lx·s with dark decays 70 and 60 V/s respectively. The introduction of chlorine atoms can improve their photoelectric properties. SEM analyses also show that the dispersion of pigment in OPC could affect its photosensitivity.
基金support from the National Natural Science Foundation of China(Nos.51962023,51862024)the Natural Science Foundation of Jiangxi Province,China(Nos.20212BAB204045,20192ACBL21047)the Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle(Nanchang Hangkong University)(No.ES202002077).
文摘The matched energy band structure and efficient carrier separation efficiency are the keys to heterogeneous photocatalytic reactions.A novel organic/inorganic step scheme(S-scheme)heterojunction PDI-Urea/BiOBr composite photocatalyst was constructed by simple solvothermal reaction combined with in-situ growth strategy.The composite photocatalyst not only has high chemical stability,but also can generate and accumulate a large number of active species(h^(+),·O_(2)^(-),·OH,H_(2)O_(2)).PDI-Urea/BiOBr showed higher photocatalytic activity for the degradation of antibiotic such as ofloxacin(OFLO),tetracycline(TC)and the production of H_(2)O_(2) in the spectral range of 400-800 nm.The apparent rate constant of 15%PDI-Urea/BiOBr for photocatalytic degradation of TC(or OFLO)was 2.7(or 2.5)times that of pure BiOBr and 1.7(or 1.8)times that of pure PDI-Urea.The H_(2)O_(2) evolution rate of 15%PDI-Urea/BiOBr was 2.5 times that of PDI-Urea and 1.5 times that of BiOBr,respectively.This work has formed a mature S-scheme heterojunction design thought and method,which offers new visions for the development of heterogeneous photocatalysts.
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 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Project(50573019)support by the National Natural Science Foundation of China
文摘An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoethyl）-piperazine. Then imidization of perylene-3, 4, 9, 10-tetracarboxylic acid dianhydride with 2,4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was carried out to afford a novel perylene derivative bearing two melamine blocks （S2） and 1, 6, 7, 12-tetra（4-tert-butyl phenoxy）-perylene-3, 4, 9, 10-tetracarboxylic acid bisimide （S1. The hydrogen-bonding interactions between S1 and S2 were investigated by IH NMR spectrum, UV/Vis spectrum and fluorescence spectrum. The influences on the morphologies of S1·S2 aggregates were investigated. The results show that well-defined nanofibers with a diameter of about 100 nm can be obtained by self-assembly between S1 and S2 only in CH2Cl2 solution. Based on these results, guidelines for the molecular design and self-assembly of supramolecular polymer materials are presented.
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%.
