Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crys...Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.展开更多
Inverted(p-i-n)perovskite solar cells(PerSCs)have attracted much attention owing to their low temperature processability,less hysteresis effect and easy integration as a subunit for the tandem device.The unsatisfactor...Inverted(p-i-n)perovskite solar cells(PerSCs)have attracted much attention owing to their low temperature processability,less hysteresis effect and easy integration as a subunit for the tandem device.The unsatisfactory interface contacts and energy level barrier between adjacent interlayers on the cathode side are one of the key challenges for the development of p-i-n PerSCs.Herein,perylene diimidebased(PDI)ionene polymer was synthesized and developed as a cathode interlayer(CIL)to enhance interface contact,reduce the energy level barrier and prevent the migration of I-ions.The compact PNPDI CIL with high conductivity and appropriate lowest unoccupied molecular orbital(LUMO)level,resulted in a high efficiency device(20.03%),which is higher than the control device with bathophenanthroline(Bphen)(19.48%).Bphen-based CIL shows better adjusting ability of the work function of cathode metal but exhibits poor film-forming property.So,the synergistic effect of 1+1>2 can be obtained by combining Bphen and PNPDI into one CIL.As expected,the device performance was further improved by using the mixed CIL of Bphen and PNPDI,and 21.46%power conversion efficiency(PCE)was achieved.What’s more,the compact and hydrophobic mixed CIL dramatically enhanced the resistance to I-ions and moisture,which led to much enhanced device stability.展开更多
Graphitic carbon nitride(g-C_(3)N_(4))is widely used in organic metal-ion batteries owing to its high porosity,facile synthesis,stability,and high-rate performance.However,pristine g-C_(3)N_(4)nanosheets exhibit poor ...Graphitic carbon nitride(g-C_(3)N_(4))is widely used in organic metal-ion batteries owing to its high porosity,facile synthesis,stability,and high-rate performance.However,pristine g-C_(3)N_(4)nanosheets exhibit poor electrical conductivity,irreversible metal-ion storage capacity,and short-term cycling owing to their high concentration of graphitic-N species.Herein,a series of 3,4:9,10-perylenetetracarboxylic diimide-coupled g-C_(3)N_(4)composite anode materials,CN-PI_(x)(x=0.2,0.5,0.75,and 1),was investigated,which exhibited an unusually high surface nitrogen content(23.19-39.92 at.%)and the highest pyridinic-N,pyrrolic-N,and graphitic-N contents reported to date.The CN-PI_(1)anode delivers an unprecedented and continuously increasing ultrahigh discharging capacity of exceeding 8400 mAh g^(-1)(1.96 mWh cm^(-2))at 100 mA g^(-1)with high specific energy density(E_(sp))of~7700 Wh kg^(-1)and the volumetric energy density(E_(v))of~14956 Wh L-1 and an excellent long-term stability(414 mAh g^(-1)or 0.579 mWh cm^(-2)at 1 A g^(-1)).Furthermore,the activation of the CN-PI_(x)electrodes contributes to their superior electrochemical performance,resulting from the fact that the Li+is not only stored in the CN-PI_(x)composites but also CN-PI_(x)activated the Li^(0)adlayer on the CN-PI_(1)-Cu heterojunction as an SEI layer to avoid the direct contact of Li^(0)phase and the electrolyte.The CN-PI_(1)full cell with LiCoO_(2)as the cathode delivers a discharge capacity of~587 mAh g^(-1)at a 1 A g^(-1)after 250 cycles with a Coulombic efficiency nearly 99%.This study provides a strategy to develop N-doped g-C_(3)N_(4)-based anode materials for realizing long-lasting energy storage devices.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
Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigate...Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigated by UV-vis and fluorescence spectroscopy. The absorption spectra of these compounds showed wide spectral responses from 300 to 700 nm, which would be potentials for application as organic solar cells.展开更多
The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G** by density functional theory. The results showed that the perylene and its four derivatives belonged to the s...The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G** by density functional theory. The results showed that the perylene and its four derivatives belonged to the semiconductor molecules, which released energy when electron was injected. Therefore, they were suitable to be used as the electron injection material. The introduction of OH group can improve the electron transfer rate significantly. The formations of intramolecular hydrogen bonds were unfavorable to the hole transfer, but conducive to the electron transfer. The perylene derivatives, 2,5-3,4,5-(trifluorophenyl)ethynyl-8,11-3,4,5-trihydroxyphenyl ethynyl, designed in this article had the hole transfer rate of 1.57 cm2/V·s·1. Therefore, this kind of material will be potential hole transfer material with high transfer efficiency.展开更多
N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A...N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.展开更多
A novel organic soluble and thermal-stable fullerene-perylene dyad, in which a perylene moietyis attached to C60, has been prepared by 1, 3-dipolar cycloaddition of the azomethine ylides generated in situ from the ald...A novel organic soluble and thermal-stable fullerene-perylene dyad, in which a perylene moietyis attached to C60, has been prepared by 1, 3-dipolar cycloaddition of the azomethine ylides generated in situ from the aldehyde and N-methylglycine and characterized by NMR, FT-IR, TGA, absorption and fluorescent spectra etc.展开更多
The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the ...The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.展开更多
Pressure can reduce the distances among atoms, thereby modifying the overall optical characteristics of molecules.In this article, the excited state behavior of perylene is carefully observed under isotropic pressure ...Pressure can reduce the distances among atoms, thereby modifying the overall optical characteristics of molecules.In this article, the excited state behavior of perylene is carefully observed under isotropic pressure and non-complexing condition. In a steady state, absorption peak shows red shift and spectral width are broadened with pressure increasing,which is ascribed to the π-electron delocalization between molecules. In a transient state, the transition dynamics presents a wavelike tendency with pressure increasing because the shift of self-tapping exciton state is contrary to that of Y-state with pressure increasing. The results conduce to understanding the influence of inter-molecule interaction on excited state behavior with inter-molecule distance decreasing, which contributes to studying the materials under extreme condition.展开更多
An asymmetrical perylene diimide 3, N-(4-methoxyphenyl)-N'-(4-nitrophenyl)-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in...An asymmetrical perylene diimide 3, N-(4-methoxyphenyl)-N'-(4-nitrophenyl)-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in detail by UV-vis and fluorescence spectroscopies. The resulting unique helical nanostructures from 3 were proposed to be self-assembled via the cooperative actions of π-π stacking, steric hindrance and electrophile-nucleophile type pairing.展开更多
A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1, 3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10^-3 cm^2/Vs, which is in th...A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1, 3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10^-3 cm^2/Vs, which is in the range of the highest values found for other promising charge transport materials suitable for solution processable technique.展开更多
The perylene (C20H12) layer effect on the electrical and dielectric properties of Al/p-Si (MS) and Al/perylene/p-Si (MPS) diodes have been investigated and compared in the frequency range of 0.7 kHz-2 MHz. Exper...The perylene (C20H12) layer effect on the electrical and dielectric properties of Al/p-Si (MS) and Al/perylene/p-Si (MPS) diodes have been investigated and compared in the frequency range of 0.7 kHz-2 MHz. Experimental results show that C-V characteristics give an anomalous peak for two structures at low frequencies due to interface states (Nss) and series resistance (Rs). The increases in C and G/o3 at low frequencies confirm that the charges at interface can easily follow an ac signal and yield excess capacitance and conductance. The frequency-dependent dielectric constant (er) and dielectric loss (e') are subtracted using C and G/co data at 1.5 V. The eI and e" values are found to be strongly dependent on frequency and voltage, and their large values at low frequencies can be attributed to the excess polarization coming from charges at traps. Plots of ln(o'ac)-ln(w) for two structures have two linear regions, with slopes of 0.369 and 1.166 for MS, and of 0.077 and 1.061 for MPS, respectively. From the C 2-V characteristics, the doping acceptor atom concentration (NA) and barrier height (,~) for Schottky barrier diodes (SBDs) 1.303 ~ 1015 cm-3, and 1.10 and I. 13 eV, respectively. of MS and MPS types are also obtained to be 1.484 ~ 1015展开更多
Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugati...Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugation are often ignored.Herein,a perylene diimide(PDI)derivative named FIDT-PDI is designed and synthesized to shed light into the effect of hyperconjugation on the molecular packing and further the photovoltaic performance.Dynamic NMR and 2D NOE NMR demonstrate the formation of intermolecularσ-πhyperconjugation between the C—H bond of the PDI moiety in one molecule and the phenyl sidechain in another molecule of FIDT-PDI.Benefiting from theσ-πhyperconjugation,FIDT-PDI with twisted backbone reversely exhibits more ordered packing and stronger crystallinity compared with another PDI derivative FIDTT-PDI which has better planarity,consequently achieving superior PCE and higher carrier mobility.This contribution is the first paradigm to unravel the structure-property relationship betweenσ-πhyper-conjugation of conjugated materials and corresponding photovoltaic performance.展开更多
Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for co...Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.展开更多
A novel polyurethane polymer containing perylene diimide(PDI)unit and aniline segment,denoted as PU-PDI,was designed and synthesized.Their tensile property and photophysical characteristic were investigated using vari...A novel polyurethane polymer containing perylene diimide(PDI)unit and aniline segment,denoted as PU-PDI,was designed and synthesized.Their tensile property and photophysical characteristic were investigated using various experimental and theoretical techniques.It is found that the elongation of PU-PDIs can reach more than 1000%,indicating good tensile performance.Moreover,based on the photoinduced electron transfer mechanism,the aniline segments in polyurethane can quench the auto-fluorescence of PDI unit to a negligible value,which overcomes the intractable fluorescence drawbacks of conventional colour filters.The non-emissive characteristic,in combination with the good thermal stability and tensile property of PU-PDI,provides a feasible design strategy to fabricate optical filters with high display quality.展开更多
Inverted perovskite solar cells(PerSCs)are a highly promising candidate in the photovoltaic field due to their low-temperature fabrication process,negligible hysteresis,and easy integration with Si-based solar cells.A...Inverted perovskite solar cells(PerSCs)are a highly promising candidate in the photovoltaic field due to their low-temperature fabrication process,negligible hysteresis,and easy integration with Si-based solar cells.A cathode interlayer(CIL)is necessary in the development of inverted devices to reduce the trap density and energy barrier between the electron transport layer(ETL)and the electrode.However,most CILs are highly thickness-sensitive due to low conductivity and poor film-forming.In this study,we report on a self-doping perylene imide-based ionene polymer(PNPDIN)used as CIL material to modify electrode in inverted PerSCs.PNPDIN exhibits high conductivity and a good solubility in polar solvent,which results in an improved power conversion efficiency(PCE)from 10.05%(device without a CIL)to 16.97%.When the blend of PNPDIN and Bphen was used as a mixed CIL,the PCE of PerSCs can be further increased to 21.28%owing to the excellent morphology and matched energy level.More importantly,the PCE of the device is highly tolerant to the thickness of the mixed CIL,which benefited from the high conductivity of PNPDIN.This development is expected to provide an excellent mixed CIL material for roll-to-roll processing efficient and stable inverted PerSCs.展开更多
By combining stable radical tetramethylpiperidine nitrogen oxide(TEMPO)as end groups and perylene bisimide(PBI)as the core,a small molecular cathode interlayer(CIL)(PBI-TEMPO)was synthesized.Detailed physical-chemical...By combining stable radical tetramethylpiperidine nitrogen oxide(TEMPO)as end groups and perylene bisimide(PBI)as the core,a small molecular cathode interlayer(CIL)(PBI-TEMPO)was synthesized.Detailed physical-chemical characterizations indicate that PBI-TEMPO can form smooth film,owns low unoccupied molecular orbital(LUMO)level of−3.67 eV and can reduce the work function of silver electrode.When using PBI-TEMPO as CIL in non-fullerene organic solar cells(OSCs),the PM6:BTP-4Cl based OSCs delivered high power conversion efficiencies(PCEs)up to 17.37%,higher than those using commercial PDINO CIL with PCEs of 16.95%.Further device characterizations indicate that PBI-TEMPO can facilitate more efficient exciton dissociation and reduce charge recombination,resulting in enhanced current density and fill factor.Moreover,PBI-TEMPO displays higher thermal stability than PDINO in solution.When PBI-TEMPO and PDINO solution were heated at 150℃ for 2 h and then were used as CIL in solar cells,PBI-TEMPO-based OSCs provided a PCE of 15%,while PDINO-based OSCs only showed a PCE of 10%.These results demonstrate that incorporating TEMPO into conjugated materials is a useful strategy to create new organic semiconductors for application in OSCs.展开更多
Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing struc...Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing structure and the radical content for carrier transport in the solid state still need to be determined.Bringing the electron-withdrawing groups is an effective strategy for enablingπ−πstacking distance.Here,bay-tetrachloro-substituted PDI(B-4Cl-PDI)anion radical and dianion films were fabricated quantitatively doped with N_(2)H_(4)·H_(2)O.The radical contents were quantitatively calculated by absorption spectra in different doping ratios.The X-ray powder diffraction patterns showed that the anion radical presented a crystalline structure,and dianion aggregates exhibited an amorphous structure.With precise manipulation of the radical content,the anion radical aggregates and dianion aggregates showed the maximum electrical conductivity value of 0.024 and 0.0018 S/cm,respectively.The experiment results show that doping level and aggregate structure play a crucial role in electronic transport properties.展开更多
Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene m...Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene monoimide(PMI)derivative incorporating large spatial phenyl-carborane was synthesized and found to exhibit unexpected photophysical properties.The structurally bent PDCB exhibits not only PMI-like emission but also a red-shifted emission.In sharp contrast,PMI-CBH,a linear PMI derivative,exhibits only PMI-like emission.Furthermore,upon local excitation,PDCB undergoes a photoinduced electron transfer(PET)between PMI and phenylcarborane,resulting in a charge-transfer state.Two other PMI derivatives,PCB and PDCBP,showed a similar phenomenon.The PET rate is in the order of PCB(48 ps^(-1))>PDCB(163 ps^(-1))>PDCBP(815 ps^(-1))in toluene,which decreases with increasing steric hindrance,inferring structure reorganization prior to the PET process.As expected,a fabricated PDCB-based sensor showed excellent performance in acetone sensing.展开更多
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB3807700Hubei Natural Science Foundation Innovation Group Project,Grant/Award Number:2022CFA020+2 种基金Joint Funds of the Hubei Natural Science Foundation Innovation and Development,Grant/Award Number:2022CFD034Major Technological Innovation Project of Hubei Science and Technology Department,Grant/Award Number:2019AAA164National Natural Science Foundation of China,Grant/Award Number:2022CFD034。
文摘Fe-based Prussian blue(Fe-PB)cathode material shows great application potential in sodium(Na)-ion batteries due to its high theoretical capacity,long cycle life,low cost,and simple preparation process.However,the crystalline water and vacancies of Fe-PB lattice,the low electrical conductivity,and the dissolution of metal ions lead to limited capacity and poor cycling stability.In this work,a perylene tetracarboxylic dianhydride amine(PTCDA)coating layer is successfully fabricated on the surface of Fe-PB by a liquid-phase method.The aminated PTCDA(PTCA)coating not only increases the specific surface area and electronic conductivity but also effectively reduces the crystalline water and vacancies,which avoids the erosion of Fe-PB by electrolyte.Consequently,the PTCA layer reduces the charge transfer resistance,enhances the Na-ion diffusion coefficient,and improves the structure stability.The PTCA-coated Fe-PB exhibits superior Na storage performance with a first discharge capacity of 145.2 mAh g^(−1) at 100 mA g^(−1).Long cycling tests exhibit minimal capacity decay of 0.027%per cycle over 1000 cycles at 1 A g^(−1).Therefore,this PTCA coating strategy has shown promising competence in enhancing the electrochemical performance of Fe-PB,which can potentially serve as a universal electrode coating strategy for Na-ion batteries.
基金supported by the National Key Research and Development Program of China(2019YFA0705201)the Heilongjiang Provincial Postdoctoral Science Foundation(LBHTZ0604)the CAS Key Laboratory of Renewable Energy,Guangzhou Institute of Energy Conversion(E229kf0901)。
文摘Inverted(p-i-n)perovskite solar cells(PerSCs)have attracted much attention owing to their low temperature processability,less hysteresis effect and easy integration as a subunit for the tandem device.The unsatisfactory interface contacts and energy level barrier between adjacent interlayers on the cathode side are one of the key challenges for the development of p-i-n PerSCs.Herein,perylene diimidebased(PDI)ionene polymer was synthesized and developed as a cathode interlayer(CIL)to enhance interface contact,reduce the energy level barrier and prevent the migration of I-ions.The compact PNPDI CIL with high conductivity and appropriate lowest unoccupied molecular orbital(LUMO)level,resulted in a high efficiency device(20.03%),which is higher than the control device with bathophenanthroline(Bphen)(19.48%).Bphen-based CIL shows better adjusting ability of the work function of cathode metal but exhibits poor film-forming property.So,the synergistic effect of 1+1>2 can be obtained by combining Bphen and PNPDI into one CIL.As expected,the device performance was further improved by using the mixed CIL of Bphen and PNPDI,and 21.46%power conversion efficiency(PCE)was achieved.What’s more,the compact and hydrophobic mixed CIL dramatically enhanced the resistance to I-ions and moisture,which led to much enhanced device stability.
基金supported by the“Human Resources Program in Energy Technology”of the Korea Institute of Energy Technology Evaluation and Planning,granted financial resources from the Ministry of Trade,Industry&Energy,Republic of Korea(Grant No.20204010600100)the Basic Science Research Program through the National Research Foundation of Korea,funded by the Ministry of Education,Republic of Korea(Grant No.NRF-2019R1I1A3A01046928).
文摘Graphitic carbon nitride(g-C_(3)N_(4))is widely used in organic metal-ion batteries owing to its high porosity,facile synthesis,stability,and high-rate performance.However,pristine g-C_(3)N_(4)nanosheets exhibit poor electrical conductivity,irreversible metal-ion storage capacity,and short-term cycling owing to their high concentration of graphitic-N species.Herein,a series of 3,4:9,10-perylenetetracarboxylic diimide-coupled g-C_(3)N_(4)composite anode materials,CN-PI_(x)(x=0.2,0.5,0.75,and 1),was investigated,which exhibited an unusually high surface nitrogen content(23.19-39.92 at.%)and the highest pyridinic-N,pyrrolic-N,and graphitic-N contents reported to date.The CN-PI_(1)anode delivers an unprecedented and continuously increasing ultrahigh discharging capacity of exceeding 8400 mAh g^(-1)(1.96 mWh cm^(-2))at 100 mA g^(-1)with high specific energy density(E_(sp))of~7700 Wh kg^(-1)and the volumetric energy density(E_(v))of~14956 Wh L-1 and an excellent long-term stability(414 mAh g^(-1)or 0.579 mWh cm^(-2)at 1 A g^(-1)).Furthermore,the activation of the CN-PI_(x)electrodes contributes to their superior electrochemical performance,resulting from the fact that the Li+is not only stored in the CN-PI_(x)composites but also CN-PI_(x)activated the Li^(0)adlayer on the CN-PI_(1)-Cu heterojunction as an SEI layer to avoid the direct contact of Li^(0)phase and the electrolyte.The CN-PI_(1)full cell with LiCoO_(2)as the cathode delivers a discharge capacity of~587 mAh g^(-1)at a 1 A g^(-1)after 250 cycles with a Coulombic efficiency nearly 99%.This study provides a strategy to develop N-doped g-C_(3)N_(4)-based anode materials for realizing long-lasting energy storage devices.
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This work was supported by National Natural Science Foundation of China and Shanghai Science Committee.
文摘Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigated by UV-vis and fluorescence spectroscopy. The absorption spectra of these compounds showed wide spectral responses from 300 to 700 nm, which would be potentials for application as organic solar cells.
基金Supported by the National Natural Science Foundation of China(No.51273133)the Opening Project of National Key Laboratory of Theoretical Chemical Computation(No.K1202)the Department of Education in Sichuan Province(No.11ZB086)
文摘The charge transfer rates of perylene and its four derivatives were studied at the level of B3LYP/6-31G** by density functional theory. The results showed that the perylene and its four derivatives belonged to the semiconductor molecules, which released energy when electron was injected. Therefore, they were suitable to be used as the electron injection material. The introduction of OH group can improve the electron transfer rate significantly. The formations of intramolecular hydrogen bonds were unfavorable to the hole transfer, but conducive to the electron transfer. The perylene derivatives, 2,5-3,4,5-(trifluorophenyl)ethynyl-8,11-3,4,5-trihydroxyphenyl ethynyl, designed in this article had the hole transfer rate of 1.57 cm2/V·s·1. Therefore, this kind of material will be potential hole transfer material with high transfer efficiency.
基金Shanghai Natural Science Foundation,China(No.13ZR1400700)The Program for Innovative Research Team in University,China(No.IRT1221)
文摘N,N'-bis( n-dodecyl)-3,4: 9,10-tetracarboxyl-diimide( 1,7-H-PDI-C12) and its bay position 1,7-Br substituted derivative have been synthesized and characterized by1H-NMR,13C-NMR,FT-IR,and X-ray diffraction( XRD). A comparison of the two samples by measuring their photo physical properties using UV visible absorption and fluorescence emission spectra revealed that bay substitutions of bromine do not have significant effect on the perylene diimide( PDI) photo physical properties in solution. However,the solid state fluorescence properties were enhanced by brominating at bay areas. The solid fluorescence quantum yield of 1,7-Br-PDI-C12 was 2. 83%( Фf= 2. 83%) and 1,7-H-PDI-C12 was only 0. 02%( Фf= 0. 02%). This behavior was also reflected in the steady-state fluorescence spectra. This work shows that solid state photo physical properties of PDI could be improved without changing the other properties by simply using bromine substitution at bay areas. These types of materials are useful intermediate for further synthesis of PDI with tunnable optoelectronic properties.
文摘A novel organic soluble and thermal-stable fullerene-perylene dyad, in which a perylene moietyis attached to C60, has been prepared by 1, 3-dipolar cycloaddition of the azomethine ylides generated in situ from the aldehyde and N-methylglycine and characterized by NMR, FT-IR, TGA, absorption and fluorescent spectra etc.
文摘The effect of fluorination on the aggregate structure of a novel fluorinated perylene diimide, N, N'-diperfluorophenyl-3, 4, 9, 10-perylenetetracarboxylic diimide 1, was investigated by UV-Vis absorptions and the conformation simulations from AM1 semi-empirical quantum mechanics modeling. The results showed that in the solid film 1 molecules stacked with the perfluorinated phenyl groups straightly over or below the perylene cores of the adjacent 1 molecules.
基金Project supported by the National Key Research and Development Program of China(Grant Nos.2018YFA0305900 and 2017YFA0403704)the National Natural Science Foundation of China(Grant Nos.61575079,51632002,11804113,and 51720105007)+1 种基金the Natural Science Foundation of Jilin Province,China(Grant No.20180101230JC)the Program for Changjiang Scholars and Innovative Research Team in University,China(Grant No.IRT 15R23).
文摘Pressure can reduce the distances among atoms, thereby modifying the overall optical characteristics of molecules.In this article, the excited state behavior of perylene is carefully observed under isotropic pressure and non-complexing condition. In a steady state, absorption peak shows red shift and spectral width are broadened with pressure increasing,which is ascribed to the π-electron delocalization between molecules. In a transient state, the transition dynamics presents a wavelike tendency with pressure increasing because the shift of self-tapping exciton state is contrary to that of Y-state with pressure increasing. The results conduce to understanding the influence of inter-molecule interaction on excited state behavior with inter-molecule distance decreasing, which contributes to studying the materials under extreme condition.
基金National Natural Science Foundation of China(Nos.50433020,50403022 and 50520150165)the developing program of Changjiang Scholar and Innovation Team from Education Department of China under Grant No.IRT0651.
文摘An asymmetrical perylene diimide 3, N-(4-methoxyphenyl)-N'-(4-nitrophenyl)-perylene-3,4,9,10-tetracarboxylic diimide, was synthesized, and its self-assembly and dissociation behaviors in chloroform was studied in detail by UV-vis and fluorescence spectroscopies. The resulting unique helical nanostructures from 3 were proposed to be self-assembled via the cooperative actions of π-π stacking, steric hindrance and electrophile-nucleophile type pairing.
基金This research was supported by the National Natural Scientific Foundation of China(No.90101008)973 project(No.2002CB613401)of the MST of P.R.China.
文摘A perylene bisimide dye covalently bonded with a hydrogen-bond formation group of 1, 3, 5-triazine-2, 4-diamine has been synthesized. Its casting films show a charge carrier mobility over 10^-3 cm^2/Vs, which is in the range of the highest values found for other promising charge transport materials suitable for solution processable technique.
文摘The perylene (C20H12) layer effect on the electrical and dielectric properties of Al/p-Si (MS) and Al/perylene/p-Si (MPS) diodes have been investigated and compared in the frequency range of 0.7 kHz-2 MHz. Experimental results show that C-V characteristics give an anomalous peak for two structures at low frequencies due to interface states (Nss) and series resistance (Rs). The increases in C and G/o3 at low frequencies confirm that the charges at interface can easily follow an ac signal and yield excess capacitance and conductance. The frequency-dependent dielectric constant (er) and dielectric loss (e') are subtracted using C and G/co data at 1.5 V. The eI and e" values are found to be strongly dependent on frequency and voltage, and their large values at low frequencies can be attributed to the excess polarization coming from charges at traps. Plots of ln(o'ac)-ln(w) for two structures have two linear regions, with slopes of 0.369 and 1.166 for MS, and of 0.077 and 1.061 for MPS, respectively. From the C 2-V characteristics, the doping acceptor atom concentration (NA) and barrier height (,~) for Schottky barrier diodes (SBDs) 1.303 ~ 1015 cm-3, and 1.10 and I. 13 eV, respectively. of MS and MPS types are also obtained to be 1.484 ~ 1015
基金supported by the Natural Science Foundation of Shanghai (21ZR1435100)Shenzhen Science and Technology Innovation Commission (2021SZVUP075)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University (SL2022MS015).
文摘Theπ-πinteraction is acknowledged as the predominant factor to determine the molecular packing in organic photovoltaic materials,while other non-covalent intermolecular interactions especially theσ-πhyperconjugation are often ignored.Herein,a perylene diimide(PDI)derivative named FIDT-PDI is designed and synthesized to shed light into the effect of hyperconjugation on the molecular packing and further the photovoltaic performance.Dynamic NMR and 2D NOE NMR demonstrate the formation of intermolecularσ-πhyperconjugation between the C—H bond of the PDI moiety in one molecule and the phenyl sidechain in another molecule of FIDT-PDI.Benefiting from theσ-πhyperconjugation,FIDT-PDI with twisted backbone reversely exhibits more ordered packing and stronger crystallinity compared with another PDI derivative FIDTT-PDI which has better planarity,consequently achieving superior PCE and higher carrier mobility.This contribution is the first paradigm to unravel the structure-property relationship betweenσ-πhyper-conjugation of conjugated materials and corresponding photovoltaic performance.
基金supported by the National Natural Science Foundation of China (No. 22171219)the Fundamental Research Funds for the Central Universities (No. xzy022021004)。
文摘Metallacycles hold great promise for fluorescence-based sensing due to their synthetic advantages and unique physicochemical properties. However, it remains highly challenging to develop a versatile methodology for constructing highly emissive metallacycles with targeted functionalities and therefore soughtafter properties. Herein, we report a general strategy to construct a series of highly emissive perylene diimide-based metallacycles via the self-assembly of perylene diimide-based tetrapyridyl ligand with different dicarboxylic ligands featuring fixed angles and cis-Pt(PEt_(3))_(2)(OTf)_(2). Single crystal X-ray diffraction analyses verify the formation of bowtie-like metallacycles with two triangular cavities. Notably, the fluorescence quantum yields of most assemblies exceed 98%, amongst the highest values for metallacycles.Additionally, such metallacycles exhibit sensitive fluorescence responses toward picric acid with a detection limit of 2.8 × 10^(-6)mol/L. This study not only provides a rational strategy for preparing highly emissive bowtie-shaped metallacycles, but also sheds light on their usage in the detection of picric acid and associated compounds.
基金supported by the National Natural Science Foundation of China(Grant Nos.21875157,22175129)the China Education Association for International Exchange(CEAlE)(No.2021102)the open foundation of State Key Laboratory of Chemical Engineering(No.SKL-ChE-20B04).
文摘A novel polyurethane polymer containing perylene diimide(PDI)unit and aniline segment,denoted as PU-PDI,was designed and synthesized.Their tensile property and photophysical characteristic were investigated using various experimental and theoretical techniques.It is found that the elongation of PU-PDIs can reach more than 1000%,indicating good tensile performance.Moreover,based on the photoinduced electron transfer mechanism,the aniline segments in polyurethane can quench the auto-fluorescence of PDI unit to a negligible value,which overcomes the intractable fluorescence drawbacks of conventional colour filters.The non-emissive characteristic,in combination with the good thermal stability and tensile property of PU-PDI,provides a feasible design strategy to fabricate optical filters with high display quality.
基金supported by the Natural Science Foundation of Heilongjiang Province(Grant No.LH2023E035)the Heilongjiang Provincial Postdoctoral Science Foundation(Grant No.LBH-TZ0604)+1 种基金the Open Fund of the State Key Laboratory of Luminescent Materials and Devices,South China University of Technology(Grant No.2022-skllmd-08)the National Key Research and Development Program of China(No.2019YFA0705201).
文摘Inverted perovskite solar cells(PerSCs)are a highly promising candidate in the photovoltaic field due to their low-temperature fabrication process,negligible hysteresis,and easy integration with Si-based solar cells.A cathode interlayer(CIL)is necessary in the development of inverted devices to reduce the trap density and energy barrier between the electron transport layer(ETL)and the electrode.However,most CILs are highly thickness-sensitive due to low conductivity and poor film-forming.In this study,we report on a self-doping perylene imide-based ionene polymer(PNPDIN)used as CIL material to modify electrode in inverted PerSCs.PNPDIN exhibits high conductivity and a good solubility in polar solvent,which results in an improved power conversion efficiency(PCE)from 10.05%(device without a CIL)to 16.97%.When the blend of PNPDIN and Bphen was used as a mixed CIL,the PCE of PerSCs can be further increased to 21.28%owing to the excellent morphology and matched energy level.More importantly,the PCE of the device is highly tolerant to the thickness of the mixed CIL,which benefited from the high conductivity of PNPDIN.This development is expected to provide an excellent mixed CIL material for roll-to-roll processing efficient and stable inverted PerSCs.
基金National Natural Science Foundation of China(Nos.92163128,52073016,52163018)the Open Project of State Key Laboratory of Organic-Inorganic Composites,China(No.oic-202201006)the Fund of the Academy of Sciences of Jiangxi Province,China(Nos.2022YJC2017,2021YSBG22034,2021YSBG22033).
文摘By combining stable radical tetramethylpiperidine nitrogen oxide(TEMPO)as end groups and perylene bisimide(PBI)as the core,a small molecular cathode interlayer(CIL)(PBI-TEMPO)was synthesized.Detailed physical-chemical characterizations indicate that PBI-TEMPO can form smooth film,owns low unoccupied molecular orbital(LUMO)level of−3.67 eV and can reduce the work function of silver electrode.When using PBI-TEMPO as CIL in non-fullerene organic solar cells(OSCs),the PM6:BTP-4Cl based OSCs delivered high power conversion efficiencies(PCEs)up to 17.37%,higher than those using commercial PDINO CIL with PCEs of 16.95%.Further device characterizations indicate that PBI-TEMPO can facilitate more efficient exciton dissociation and reduce charge recombination,resulting in enhanced current density and fill factor.Moreover,PBI-TEMPO displays higher thermal stability than PDINO in solution.When PBI-TEMPO and PDINO solution were heated at 150℃ for 2 h and then were used as CIL in solar cells,PBI-TEMPO-based OSCs provided a PCE of 15%,while PDINO-based OSCs only showed a PCE of 10%.These results demonstrate that incorporating TEMPO into conjugated materials is a useful strategy to create new organic semiconductors for application in OSCs.
基金National Key R&D Program of China(No.2020YFA0714604)National Natural Science Foundation of China(Nos.U20A6002,91833304,5152100222005107,52203221)+4 种基金Basic and Applied Basic Research Major Program of Guangdong Province,China(No.2019B030302007)Research and Development Funds for Science and Technology Program of Guangzhou,China(No.202007020004)Natural Science Foundation of Guangdong Province,China(Nos.2019B121205002,2022A1515010063)Fund of the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,China(No.2019B030301003)Funding by Science and Technology Projects in Guangzhou,China(Nos.202102020401,202102020561).
文摘Due to their unique physicochemical properties,the anion radical and dianion of perylene diimide derivatives(PDIs)recently attracted significant attention for organic semiconductors.However,the impact of packing structure and the radical content for carrier transport in the solid state still need to be determined.Bringing the electron-withdrawing groups is an effective strategy for enablingπ−πstacking distance.Here,bay-tetrachloro-substituted PDI(B-4Cl-PDI)anion radical and dianion films were fabricated quantitatively doped with N_(2)H_(4)·H_(2)O.The radical contents were quantitatively calculated by absorption spectra in different doping ratios.The X-ray powder diffraction patterns showed that the anion radical presented a crystalline structure,and dianion aggregates exhibited an amorphous structure.With precise manipulation of the radical content,the anion radical aggregates and dianion aggregates showed the maximum electrical conductivity value of 0.024 and 0.0018 S/cm,respectively.The experiment results show that doping level and aggregate structure play a crucial role in electronic transport properties.
基金the Ministry of Science and Technology of China(grant nos.SQ2022YFA1200081 and 2022010133)the National Natural Science Foundation of China(grant nos.21820102005 and 22132002)111 project(grant no.B14041).
文摘Innovative design of sensing fluorophores possessing superior photophysical properties,porosity,and packing-resistance structures is pivotal for high performance film-based fluorescent sensors.Herein,PDCB,a perylene monoimide(PMI)derivative incorporating large spatial phenyl-carborane was synthesized and found to exhibit unexpected photophysical properties.The structurally bent PDCB exhibits not only PMI-like emission but also a red-shifted emission.In sharp contrast,PMI-CBH,a linear PMI derivative,exhibits only PMI-like emission.Furthermore,upon local excitation,PDCB undergoes a photoinduced electron transfer(PET)between PMI and phenylcarborane,resulting in a charge-transfer state.Two other PMI derivatives,PCB and PDCBP,showed a similar phenomenon.The PET rate is in the order of PCB(48 ps^(-1))>PDCB(163 ps^(-1))>PDCBP(815 ps^(-1))in toluene,which decreases with increasing steric hindrance,inferring structure reorganization prior to the PET process.As expected,a fabricated PDCB-based sensor showed excellent performance in acetone sensing.