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
The key building blocks,tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides(Si-TDIs and 2Si-TDIs)were synthesized for the first time.Single-crystal analysis verified the almost plana...The key building blocks,tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides(Si-TDIs and 2Si-TDIs)were synthesized for the first time.Single-crystal analysis verified the almost planar molecular configurations of both Si-TDIs and 2Si-TDIs.They exhibited intriguing optical properties including red-shifted absorption and near-infrared emission properties with excellent fluorescence quantum yields,as well as precisely controlled HOMO/LUMO energy levels by Si-heteroannulation.The single-crystal organic field-effect transistors based on 2Si-TDI 5a featuring long and branched alkyl chains demonstrated well-balanced ambipolar transporting properties with electron/hole mobilities of 0.10/0.18 cm2 V^(−1)s^(−1).展开更多
Aggregation-induced emission enhancement and aggregation-induced chirality inversion are two individ-ual phenomena for the enantiomerically pure organic dyes in the aggregates.Herein we reported for the first time tha...Aggregation-induced emission enhancement and aggregation-induced chirality inversion are two individ-ual phenomena for the enantiomerically pure organic dyes in the aggregates.Herein we reported for the first time that these two interesting phenomena could be observed simultaneously in the aggregated states of enantiomerically pure S/R-1,1?-binaphthol annulated perylene diimides,in which two perylene diimides moieties were bridged by S/R-1,1?-binaphthol(BINOL)at the bay positions.Owing to the rotat-able C2 axes between two naphthol annulated perylene diimides moieties,both of them display intrinsic behaviors of aggregation-induced emission enhancements.At the same time,due to the steric hindrances in the imide and methoxy positions,the neighboring twoπ-systems of these two unique polycyclic aro-matic imides in poor solvents are preferable to adopt a cross-stacking mode and thus form helical X-aggregates of opposite chirality(M/P)with chirality inversion characteristics in their circular dichroism and circularly polarized luminescence spectroscopic studies.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
The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysi...The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysical properties of the functionalized dyes were investigated in solution and solid state by UV-vis and photoluminescence（PL） spectra.Their UV-vis and PL spectrum both exhibited the different concentration-dependent behaviors due to the difference of chemical structure.Moreover,cyclic voltammetry results indicated that the introduction of oxygen bridged twisted heptatomic biphenyl could decrease the LUMO energy level of the perylene diimide effectively and made it promising material in photoelectric devices.展开更多
Azaacene diimides are expected to possess deeplowest unoccupied molecular orbital (LUMO) levelsand narrower bandgaps while maintaining excellentsolubility and enhanced stability compared to theirparent acenes. However...Azaacene diimides are expected to possess deeplowest unoccupied molecular orbital (LUMO) levelsand narrower bandgaps while maintaining excellentsolubility and enhanced stability compared to theirparent acenes. However, the synthesis of fully conjugatedazaacenes has posed a long-term challenge. Inthis study, we report a stepwise oxidation approachto successfully synthesize a series of fully conjugatedtetraazahexacene diimides (TAHDIs). Through peripheryengineering, the targeted TAHDIs, featuringelectron-donating ethylenedioxy rings, exhibitedsignificantly enhanced stability, with a half-life time(τ1/2) of up to 65 h under ambient conditions.Furthermore, single-crystal structural elucidationrevealed a nearly planar geometry, with the imiderings slightly deviating from the skeleton plane. Notably,the LUMO levels were determined to be as lowas −4.68 eV for TAHDI-ad and could be noticeablyelevated to −4.53 eV through the attachment ofelectron-donating groups (TAHDI-ce). This workrepresents a rare example of an experimetally evidencedlow-lying LUMO level, providing an alternativestrategy for developing higher fully conjugatedazacene diimides, which have great promise in electronicsand molecular electronics.展开更多
Perylene-diimide(PDI)-based NFA could be synthesized via a few steps with high yields,and exhibit outstanding chemical robustness and photostability,which is suitable for the commercialization of organic solar cells(O...Perylene-diimide(PDI)-based NFA could be synthesized via a few steps with high yields,and exhibit outstanding chemical robustness and photostability,which is suitable for the commercialization of organic solar cells(OSCs).Nowadays,the power conversion efficiency(PCE)of PDI-based OSCs has exceeded 11%and run into the bottleneck.It is time to summarize the latest achievements and find the clue to overcome the challenges for further improving the PCE of PDI-based OSCs.In this review,we summarize the latest achievements in PDI-based OSCs and highlight those potential strategies for further improving the photovoltaic performance of PDI-based OSCs,including fine-tuning the stacking behaviors and absorption spectra of PDI-based NFAs and the developments of narrow bandgap donor materials which are compatible with PDI-based NFAs.New record of PCE is anticipated and new application of PDI-based OSCs worths exploring.展开更多
The incorporation of heavy atoms into molecular backbone is an extremely straightforward strategy for fine-tuning the optoelectronic properties of organic semiconductors.However,it is rarely studied in n-type small mo...The incorporation of heavy atoms into molecular backbone is an extremely straightforward strategy for fine-tuning the optoelectronic properties of organic semiconductors.However,it is rarely studied in n-type small molecules.Herein,by selenium substitution of NDI3 HU-DTYM2,two Se-decorated core-expanded naphthalene diimides(NDI)derivatives DTYM-NDI3 HUDSYM(1)and NDI3 HU-DSYM2(2)were synthesized.In comparison with the reference S-containing compound NDI3 HUDTYM2,the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)energy levels of 1 and 2 were fine-tuned with?HOMO of about 0.2 e V,?LUMO of 0.1 e V and the narrowed HOMO-LUMO gaps.More surprisingly,the as-spun organic thin film transistors(OTFTs)based on 1 and 2 both showedμe,satvalues as high as1.0 cm2 V-1 s-1,which are 2-fold higher than that of NDI3 HU-DTYM2 with the same device structure and measurement conditions.In addition,the single crystal OFET devices based on Se-containing compound NDI2 BO-DSYM2 showed a highμe,satvalue of 1.30 cm2 V-1 s-1.The molecular packing of NDI2 BO-DSYM2 in single crystals(two-dimensional supramolecular structure formed by intermolecular Se···Se interactions)is quite different from that of a S-containing compound NDI-DTYM2(one dimensional supramolecular structure formed by intermolecularπ-πstacking).Therefore,the Se substitution can cause dramatic change about molecular stacking model,giving rise to high n-type OTFT performance.Our results demonstrated an effective strategy of the heavy atom effect for designing novel organic semiconductors.展开更多
Terrylene diimides with four aromatic heterocycles(AHTDIs)were synthesized under Stille Cross-coupling conditions and fully characterized by NMR and mass spectrometry.The aggregation of the terrylene diimide(TDI)was s...Terrylene diimides with four aromatic heterocycles(AHTDIs)were synthesized under Stille Cross-coupling conditions and fully characterized by NMR and mass spectrometry.The aggregation of the terrylene diimide(TDI)was suppressed by four heterocycles substituents on the bay region,and these AHTDIs exhibited good solubility in common organic solvents.The effects of the substituted groups on the optical and electrochemical properties were also investigated.The introduction of four aromatic heterocycles on the bay of TDI resulted in significant red-shifts of the absorption peak(100 nm),corresponding to a decrease in the band gap from 1.82 to 1.50 eV.Furthermore,with four rich electron aromatic heterocycles,the AHTDIs showed 280 mV negative-shifts of first oxidation poten-tials and a new oxidation wave,corresponding to an increase in the HOMO levels from−5.60 to−5.28 eV.展开更多
Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared f...Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared fluorescence quantum yield(Φ_(FL))and fluorescent brightness remain a significant challenge owing to the energy gap law.Herein,we developed a straightforward and effective chalcogen-annulation strategy by introducing O,S and Se into the bay region of TDI and QDI fluorophores,realizing the increase ofΦFLand fluorescent brightness up to 10 times.To our best knowledge,this study potentially stands as the pioneering instance showcasing the anti-heavy-atom effect of chalcogens,and the absoluteΦFL(93%)and fluorescent brightness(128,200 cm^(-1)mol^(-1)L)of Se-TDI is among top deep-red/near-infrared organic fluorophores currently available.The femtosecond transient absorption(fs-TA)measurements show the absence of obvious changes of the excited state lifetime after the introduction of chalcogens in TDI and QDI fluorophores,indicating that intersystem crossing(ISC)can be neglected in TDI and QDI fluorophores.Theoretical calculations further reveal the chalcogen-annulation strategy increase the radiative rates and reduce the reorganization energy of several accepting modes at the ground state in TDI fluorophores,leading to the suppression of internal conversion(IC)processes.Our chalcogen-annulation strategy,which effectively increases the Φ_(FL)and restricts the IC processes,while remaining unaffected by the heavy-atom effect,offers novel insights and theoretical support for the design and synthesis of deep-red/near-infrared organic fluorophores with high Φ_(FL)and fluorescent brightness.展开更多
Four classes of core-expanded naphthalene diimides （la, lb, 2a, 2b, 3 and 4） that bear different elec- tron-deficient sulfur heterocycles were designed and synthesized. The solution-processed thin films of la, 2a, 3...Four classes of core-expanded naphthalene diimides （la, lb, 2a, 2b, 3 and 4） that bear different elec- tron-deficient sulfur heterocycles were designed and synthesized. The solution-processed thin films of la, 2a, 3 and 4 operated well in air as n-channel organic transistors with electron mobility ranging from MO 6 to 0.14 cm2/Vs, depending on the different conjugated backbones. The thin film microstructure studies were also carried out to un- derstand the variations of the electron mobility for thin films of la, 2a, 3 and 4.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
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
Perylene diimide(PDI)derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient,excellent thermal and photostability,and versatile structural tunability.H...Perylene diimide(PDI)derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient,excellent thermal and photostability,and versatile structural tunability.However,due to its intrinsic rigid planar structure,π-πstacking is easy to occur,resulting in aggregation-caused quenching(ACQ).In recent years,extensive efforts have been devoted to overcome this challenge and enhance the fluorescence performance of PDIs.This review systematically summarizes representative strategies from three major perspectives:(i)Rational molecular design,including the introduction of bulky aromatic substituents,dendritic or polyhedral oligomeric silsesquioxane(POSS)units to provide steric hindrance,as well as the activation of aggregation-induced emission(AIE);(ii)Polymer-based regulation strategies,including physical blending with polymer hosts and covalent integration into polymer backbones,which provide spatial isolation and structural robustness;and(iii)Supramolecular assembly,where host-vip inclusion and self-assembly pathways precisely tune intermolecular packing and excitonic coupling.These strategies have enabled significant improvements in fluorescence quantum yield(FLQY)across solution,aggregate,and solid states.Furthermore,highly emissive perylene diimide(PDI)derivatives have demonstrated broad applicability in biomedicine,sensing and anti-counterfeiting,and optoelectronic devices such as organic light-emitting diodes(OLEDs).This review highlights the fundamental design principles,performance optimization strategies,and emerging application frontiers of PDI-based luminescent materials,providing guidance for their further development toward multifunctional and sustainable optoelectronic technologies.展开更多
With the continuous improvement of photovoltaic efficiency in the organic photovoltaic(OPV),interface engineering has emerged as a pivotal issue in their practical deployment.Currently,the robust crystallinity of smal...With the continuous improvement of photovoltaic efficiency in the organic photovoltaic(OPV),interface engineering has emerged as a pivotal issue in their practical deployment.Currently,the robust crystallinity of small molecule electron transport layers(ETLs)and the poor film-forming abilities of conjugated polymer ETLs are a huge obstacle in this field.Herein,an innovative and efficient nonconjugated polymer ETL,namely PNDI-SO,which contains polar cationic segments for solubility and conjugated units for efficient charge transport in stable OPV cells,is reported.Endowed with suitable energy levels and excellent electron extraction capabilities,PNDI-SO-based OPV cells attain a power conversion efficiency(PCE)of 18.54%.Furthermore,compared with conventional OPV cells utilizing PFN-Br or PDINN,PNDI-SO substantially enhances long-term stability under continuous illumination,evidenced by a T80 lifetime(signifying retention of 80% of initial performance)exceeding 1250 h.Notably,through scanning electron microscope,we verified that PNDI-SO achieves a harmonious balance between film-forming ability and charge transport properties for ETL,enabling the blade-coating OPV based on PBDB-TF:BTP-eC9 to achieve a PCE of 17.47%.These results suggest the potential of PNDI-SO as a promising interface material for industrial printing applications in OPV fabrication.展开更多
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This work was financially supported by the National Natural Science Foundation of China(NSFC,Nos.21901138,21790361 and 22122503)the Shandong Provincial Natural Science Foundation(No.ZR2019ZD50)China Fundamental Research Funds for the Central Universities(No.2-9-2020-041).
文摘The key building blocks,tetrachlorinated terrylene diimides and the targeted sila-annulated terrylene diimides(Si-TDIs and 2Si-TDIs)were synthesized for the first time.Single-crystal analysis verified the almost planar molecular configurations of both Si-TDIs and 2Si-TDIs.They exhibited intriguing optical properties including red-shifted absorption and near-infrared emission properties with excellent fluorescence quantum yields,as well as precisely controlled HOMO/LUMO energy levels by Si-heteroannulation.The single-crystal organic field-effect transistors based on 2Si-TDI 5a featuring long and branched alkyl chains demonstrated well-balanced ambipolar transporting properties with electron/hole mobilities of 0.10/0.18 cm2 V^(−1)s^(−1).
基金supported by the National Natural Sci-ence Foundation of China(No.21971041)Natural Science Foundation of Fujian Province(No.2020J01447).
文摘Aggregation-induced emission enhancement and aggregation-induced chirality inversion are two individ-ual phenomena for the enantiomerically pure organic dyes in the aggregates.Herein we reported for the first time that these two interesting phenomena could be observed simultaneously in the aggregated states of enantiomerically pure S/R-1,1?-binaphthol annulated perylene diimides,in which two perylene diimides moieties were bridged by S/R-1,1?-binaphthol(BINOL)at the bay positions.Owing to the rotat-able C2 axes between two naphthol annulated perylene diimides moieties,both of them display intrinsic behaviors of aggregation-induced emission enhancements.At the same time,due to the steric hindrances in the imide and methoxy positions,the neighboring twoπ-systems of these two unique polycyclic aro-matic imides in poor solvents are preferable to adopt a cross-stacking mode and thus form helical X-aggregates of opposite chirality(M/P)with chirality inversion characteristics in their circular dichroism and circularly polarized luminescence spectroscopic studies.
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.
基金supported by the National Natural Science Foundation of China (Nos: 51173155,51472214)the Colleges and Universities Science and Technology Research Project of Hebei Province (No.QN20131070)
文摘The perylene diimide derivatives（s-THBPDI and d-THBPDI） bearing oxygen bridged twisty heptatomic biphenyl in the bay positions of the perylene core through acetylene bond were designed and synthesized.The photophysical properties of the functionalized dyes were investigated in solution and solid state by UV-vis and photoluminescence（PL） spectra.Their UV-vis and PL spectrum both exhibited the different concentration-dependent behaviors due to the difference of chemical structure.Moreover,cyclic voltammetry results indicated that the introduction of oxygen bridged twisted heptatomic biphenyl could decrease the LUMO energy level of the perylene diimide effectively and made it promising material in photoelectric devices.
基金supported financially by the National Natural Science Foundation of China(NSFC,grant nos.22235005 and 22122503).
文摘Azaacene diimides are expected to possess deeplowest unoccupied molecular orbital (LUMO) levelsand narrower bandgaps while maintaining excellentsolubility and enhanced stability compared to theirparent acenes. However, the synthesis of fully conjugatedazaacenes has posed a long-term challenge. Inthis study, we report a stepwise oxidation approachto successfully synthesize a series of fully conjugatedtetraazahexacene diimides (TAHDIs). Through peripheryengineering, the targeted TAHDIs, featuringelectron-donating ethylenedioxy rings, exhibitedsignificantly enhanced stability, with a half-life time(τ1/2) of up to 65 h under ambient conditions.Furthermore, single-crystal structural elucidationrevealed a nearly planar geometry, with the imiderings slightly deviating from the skeleton plane. Notably,the LUMO levels were determined to be as lowas −4.68 eV for TAHDI-ad and could be noticeablyelevated to −4.53 eV through the attachment ofelectron-donating groups (TAHDI-ce). This workrepresents a rare example of an experimetally evidencedlow-lying LUMO level, providing an alternativestrategy for developing higher fully conjugatedazacene diimides, which have great promise in electronicsand molecular electronics.
基金supported by the National Natural Science Foundation of China(52273195,51973169)the Young Top-notch Talent Cultivation Program of Hubei Province+2 种基金the Natural Science Foundation of Hubei Province(2022CFB097)the Innovation Fund of Hubei Key Laboratory of Plasma Chemistry and Advanced Materialsthe Graduate Innovative Fund of Wuhan Institute of Technology(CX2023064)。
文摘Perylene-diimide(PDI)-based NFA could be synthesized via a few steps with high yields,and exhibit outstanding chemical robustness and photostability,which is suitable for the commercialization of organic solar cells(OSCs).Nowadays,the power conversion efficiency(PCE)of PDI-based OSCs has exceeded 11%and run into the bottleneck.It is time to summarize the latest achievements and find the clue to overcome the challenges for further improving the PCE of PDI-based OSCs.In this review,we summarize the latest achievements in PDI-based OSCs and highlight those potential strategies for further improving the photovoltaic performance of PDI-based OSCs,including fine-tuning the stacking behaviors and absorption spectra of PDI-based NFAs and the developments of narrow bandgap donor materials which are compatible with PDI-based NFAs.New record of PCE is anticipated and new application of PDI-based OSCs worths exploring.
基金the National Natural Science Foundation of China(21522209,21790362,21502218)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12010100)the Science and Technology Commission of Shanghai Municipality(19XD1424700,18JC1410600)。
文摘The incorporation of heavy atoms into molecular backbone is an extremely straightforward strategy for fine-tuning the optoelectronic properties of organic semiconductors.However,it is rarely studied in n-type small molecules.Herein,by selenium substitution of NDI3 HU-DTYM2,two Se-decorated core-expanded naphthalene diimides(NDI)derivatives DTYM-NDI3 HUDSYM(1)and NDI3 HU-DSYM2(2)were synthesized.In comparison with the reference S-containing compound NDI3 HUDTYM2,the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)energy levels of 1 and 2 were fine-tuned with?HOMO of about 0.2 e V,?LUMO of 0.1 e V and the narrowed HOMO-LUMO gaps.More surprisingly,the as-spun organic thin film transistors(OTFTs)based on 1 and 2 both showedμe,satvalues as high as1.0 cm2 V-1 s-1,which are 2-fold higher than that of NDI3 HU-DTYM2 with the same device structure and measurement conditions.In addition,the single crystal OFET devices based on Se-containing compound NDI2 BO-DSYM2 showed a highμe,satvalue of 1.30 cm2 V-1 s-1.The molecular packing of NDI2 BO-DSYM2 in single crystals(two-dimensional supramolecular structure formed by intermolecular Se···Se interactions)is quite different from that of a S-containing compound NDI-DTYM2(one dimensional supramolecular structure formed by intermolecularπ-πstacking).Therefore,the Se substitution can cause dramatic change about molecular stacking model,giving rise to high n-type OTFT performance.Our results demonstrated an effective strategy of the heavy atom effect for designing novel organic semiconductors.
基金This work was supported by Hebei Province for Dis-tinguished Young Scholar(No.B2012201031)the Na-tional Natural Science Foundation of China(No.21274036)+1 种基金the Program for New Century Excellent Talents in University(No.NCET-12-0684)Training Program for Innovative Research Team and Leading talent in Hebei Province University(No.LJRC024).
文摘Terrylene diimides with four aromatic heterocycles(AHTDIs)were synthesized under Stille Cross-coupling conditions and fully characterized by NMR and mass spectrometry.The aggregation of the terrylene diimide(TDI)was suppressed by four heterocycles substituents on the bay region,and these AHTDIs exhibited good solubility in common organic solvents.The effects of the substituted groups on the optical and electrochemical properties were also investigated.The introduction of four aromatic heterocycles on the bay of TDI resulted in significant red-shifts of the absorption peak(100 nm),corresponding to a decrease in the band gap from 1.82 to 1.50 eV.Furthermore,with four rich electron aromatic heterocycles,the AHTDIs showed 280 mV negative-shifts of first oxidation poten-tials and a new oxidation wave,corresponding to an increase in the HOMO levels from−5.60 to−5.28 eV.
基金financially supported by the National Natural Science Foundation of China(NSFC)(22235005)the National Postdoctoral Program for Innovative Talents(BX20200128)+3 种基金the 69th batch of Chinese postdoctoral general support(2021M691004)Shanghai Municipal Science and Technology Major Project(2018SHZDZX03)the Fundamental Research Funds for the Central Universitiesthe Programme of Introducing Talents of Discipline to Universities(B16017)。
文摘Deep-red/near-infrared fluorescence is highly suitable for bioimaging owing to its ability to deeply penetrate tissues,organs,and live animals.However,developing organic fluorophores with high deep-red/near-infrared fluorescence quantum yield(Φ_(FL))and fluorescent brightness remain a significant challenge owing to the energy gap law.Herein,we developed a straightforward and effective chalcogen-annulation strategy by introducing O,S and Se into the bay region of TDI and QDI fluorophores,realizing the increase ofΦFLand fluorescent brightness up to 10 times.To our best knowledge,this study potentially stands as the pioneering instance showcasing the anti-heavy-atom effect of chalcogens,and the absoluteΦFL(93%)and fluorescent brightness(128,200 cm^(-1)mol^(-1)L)of Se-TDI is among top deep-red/near-infrared organic fluorophores currently available.The femtosecond transient absorption(fs-TA)measurements show the absence of obvious changes of the excited state lifetime after the introduction of chalcogens in TDI and QDI fluorophores,indicating that intersystem crossing(ISC)can be neglected in TDI and QDI fluorophores.Theoretical calculations further reveal the chalcogen-annulation strategy increase the radiative rates and reduce the reorganization energy of several accepting modes at the ground state in TDI fluorophores,leading to the suppression of internal conversion(IC)processes.Our chalcogen-annulation strategy,which effectively increases the Φ_(FL)and restricts the IC processes,while remaining unaffected by the heavy-atom effect,offers novel insights and theoretical support for the design and synthesis of deep-red/near-infrared organic fluorophores with high Φ_(FL)and fluorescent brightness.
基金The present research was financially supported by National Natural Science Foundation of China，the Ministry of Science and Technology，the Chinese Academy of Sciences
文摘Four classes of core-expanded naphthalene diimides （la, lb, 2a, 2b, 3 and 4） that bear different elec- tron-deficient sulfur heterocycles were designed and synthesized. The solution-processed thin films of la, 2a, 3 and 4 operated well in air as n-channel organic transistors with electron mobility ranging from MO 6 to 0.14 cm2/Vs, depending on the different conjugated backbones. The thin film microstructure studies were also carried out to un- derstand the variations of the electron mobility for thin films of la, 2a, 3 and 4.
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.
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 National Natural Science Foundation of China(Nos.22175129,22475149)the International Sci-Tech Cooperation Project under the“Innovation Yongjiang 2035”Key R&D Programme of Ningbo Municipality(No.2024H017).
文摘Perylene diimide(PDI)derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient,excellent thermal and photostability,and versatile structural tunability.However,due to its intrinsic rigid planar structure,π-πstacking is easy to occur,resulting in aggregation-caused quenching(ACQ).In recent years,extensive efforts have been devoted to overcome this challenge and enhance the fluorescence performance of PDIs.This review systematically summarizes representative strategies from three major perspectives:(i)Rational molecular design,including the introduction of bulky aromatic substituents,dendritic or polyhedral oligomeric silsesquioxane(POSS)units to provide steric hindrance,as well as the activation of aggregation-induced emission(AIE);(ii)Polymer-based regulation strategies,including physical blending with polymer hosts and covalent integration into polymer backbones,which provide spatial isolation and structural robustness;and(iii)Supramolecular assembly,where host-vip inclusion and self-assembly pathways precisely tune intermolecular packing and excitonic coupling.These strategies have enabled significant improvements in fluorescence quantum yield(FLQY)across solution,aggregate,and solid states.Furthermore,highly emissive perylene diimide(PDI)derivatives have demonstrated broad applicability in biomedicine,sensing and anti-counterfeiting,and optoelectronic devices such as organic light-emitting diodes(OLEDs).This review highlights the fundamental design principles,performance optimization strategies,and emerging application frontiers of PDI-based luminescent materials,providing guidance for their further development toward multifunctional and sustainable optoelectronic technologies.
基金the National Natural Science Foundation of China(52303218 and 52303222)the China Postdoctoral Science Foundation(2022M720314)+1 种基金the Natural Science Foundation of Fujian Province(2023J01403)the Beijing Postdoctoral Science Foundation(2023-zz-101)for funding。
文摘With the continuous improvement of photovoltaic efficiency in the organic photovoltaic(OPV),interface engineering has emerged as a pivotal issue in their practical deployment.Currently,the robust crystallinity of small molecule electron transport layers(ETLs)and the poor film-forming abilities of conjugated polymer ETLs are a huge obstacle in this field.Herein,an innovative and efficient nonconjugated polymer ETL,namely PNDI-SO,which contains polar cationic segments for solubility and conjugated units for efficient charge transport in stable OPV cells,is reported.Endowed with suitable energy levels and excellent electron extraction capabilities,PNDI-SO-based OPV cells attain a power conversion efficiency(PCE)of 18.54%.Furthermore,compared with conventional OPV cells utilizing PFN-Br or PDINN,PNDI-SO substantially enhances long-term stability under continuous illumination,evidenced by a T80 lifetime(signifying retention of 80% of initial performance)exceeding 1250 h.Notably,through scanning electron microscope,we verified that PNDI-SO achieves a harmonious balance between film-forming ability and charge transport properties for ETL,enabling the blade-coating OPV based on PBDB-TF:BTP-eC9 to achieve a PCE of 17.47%.These results suggest the potential of PNDI-SO as a promising interface material for industrial printing applications in OPV fabrication.
