Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substit...Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.展开更多
Two perylene bisimides based non-fullerene small molecules, H-DIPBI and B-DIPBI, are applied into inverted planar heterojunction perovskite solar cells. The power conversion efficiency up to 11.6% has been achieved fo...Two perylene bisimides based non-fullerene small molecules, H-DIPBI and B-DIPBI, are applied into inverted planar heterojunction perovskite solar cells. The power conversion efficiency up to 11.6% has been achieved for device with B-DIPBI,indicating that non-fullerene acceptor can function as the electron transport layer to replace PCBM in perovskite solar cells.展开更多
An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoet...An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoethyl）-piperazine. Then imidization of perylene-3, 4, 9, 10-tetracarboxylic acid dianhydride with 2,4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was carried out to afford a novel perylene derivative bearing two melamine blocks （S2） and 1, 6, 7, 12-tetra（4-tert-butyl phenoxy）-perylene-3, 4, 9, 10-tetracarboxylic acid bisimide （S1. The hydrogen-bonding interactions between S1 and S2 were investigated by IH NMR spectrum, UV/Vis spectrum and fluorescence spectrum. The influences on the morphologies of S1·S2 aggregates were investigated. The results show that well-defined nanofibers with a diameter of about 100 nm can be obtained by self-assembly between S1 and S2 only in CH2Cl2 solution. Based on these results, guidelines for the molecular design and self-assembly of supramolecular polymer materials are presented.展开更多
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
Perylene bisimide （PBI） unit has been widely used to design conjugated materials, which can be used as electron acceptor in organic solar ceils due to its strong electron-deficient ability. In this work, a conjugate...Perylene bisimide （PBI） unit has been widely used to design conjugated materials, which can be used as electron acceptor in organic solar ceils due to its strong electron-deficient ability. In this work, a conjugated polymer based on PBI dimer as monomer was designed, synthesized, and compared to the conjugated polymer containing single PBI as repeating units. The two conjugated polymers were found to have similar molecular weight, absorption spectra and energy levels. Density functional theory calculation revealed that the PBI dimer-based polymer exhibited highly twisted conjugated backbone due to the large dihedral angle between the two PBI units. The PBI-based polymers as electron acceptor were applied into polymer-polymer solar cells, in which PBI dimer-based polymer solar cells were found to show a high short circuit current density （Jsc = 11.2 mA.cm-2） and a high power conversion efficiency （PCE） of 4.5%. In comparison, the solar cells based on PBI-based polymer acceptor only provided a dsc of 7.2 mA.cm-2 and PCE of 2.5%. The significantly enhanced PCE in PBI dimer-based solar cells was attributed to the mixed phase in blended thin films, as revealed by atom force microscopy. This study demonstrates that PB! dimer can be used to design polymer acceptors for high performance polymer- polymer solar cells.展开更多
In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were fou...In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies(PCEs) up to 4.27% due to the high short-circuit current density(Jsc) of 8.52 mA/cm^2 and fill factor(FF) of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.展开更多
N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization...N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4＇-difluorodiphenylsulfone and disodium 3,3＇-disulfonate4,4＇-difluorodiphenylsulfone gave ion-exchange sulfonated poly（ether sulfone）. The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.展开更多
Designed and synthesized a new highly water soluble N,N^1-bis（2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethyl）-perylene -3,4,9,10-tetracarboxylic diimide from 2-（（5-（（dimethylamino）methyl）fura...Designed and synthesized a new highly water soluble N,N^1-bis（2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethyl）-perylene -3,4,9,10-tetracarboxylic diimide from 2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethanamine and perylene-3,4,9,10- tetracarboxylic dianhydride.The compound was characterized by ~1H,^（13）C,2D NMR,mass and IR techniques.The compound is highly fluorescent with good solubility in water and other polar solvents.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
Head-to-tail bonded perylene bisimide(PBI)dyads with different branched alkyl chains substituted at the terminal imide position show various stacking modes,which results in different effects on the excitonic processes...Head-to-tail bonded perylene bisimide(PBI)dyads with different branched alkyl chains substituted at the terminal imide position show various stacking modes,which results in different effects on the excitonic processes and electron transportation.The dyad bearing branched alkyl chains with the branching sites close to the imide positions forms homogeneously amorphous state,while with branching sites being away from the imide positions the PBI core tend to stack with multiple modes.There are fewer energy trapping sites in the homogeneously amorphous state,but in the multiple stacking system the strongπ-πinteractions give more trapping sites.Our study demonstrates that the aggregation state of PBI-based acceptors plays an important role in the performances of organic solar cells(OSCs).Multiple stacking needs to be diminished to avoid the constrained exciton dissociation and retarded charge transport in the active layer.展开更多
Fourfold benzocyclobutene-functionalized perylene bisimide（PBI 4） has been synthesized and its structure was characterized by FTIR,MS and NMR.PBI 4 can react either with itself,or the appropriate dienophiles to form...Fourfold benzocyclobutene-functionalized perylene bisimide（PBI 4） has been synthesized and its structure was characterized by FTIR,MS and NMR.PBI 4 can react either with itself,or the appropriate dienophiles to form the corresponding products under appropriate temperature.The polymer film obtained from the reaction of PBI 4 with methyl vinyl silicone rubber possessed excellent film forming properties including flatness.The optical properties of PBI 4 and polymer film obtained from the reaction of PBI 4 and methyl vinyl silicone rubber have been determined by UV/vis and fluorescence spectroscopy.展开更多
A novel perylene tetracarboxylic acid bisimide（PTCBI） in-chain polyethylene（PE） was first prepared via acyclic diene metathesis（ADMET） polymerization of PTCBI-functionalized α,ω-diene monomer. The polymers cou...A novel perylene tetracarboxylic acid bisimide（PTCBI） in-chain polyethylene（PE） was first prepared via acyclic diene metathesis（ADMET） polymerization of PTCBI-functionalized α,ω-diene monomer. The polymers could spontaneously self-assemble into hollow cylindrical structures in which the π-π interaction between adjacent PTCBI moieties was enhanced and the electron mobility was possibly promoted. The hydrogenation of as-obtained polymer was readily accomplished, affording the desired precision PTCBI in-chain PE with a saturated backbone, which showed high glass transition temperature（Tg = 63 °C）, relatively wide range of light absorption（λ = 200-575 nm）, and higher LUMO level（-3.62 e V）. It can therefore serve as a superior model for facile construction of functional polyolefin and soluble PTCBI polymer with ordered architecture.展开更多
Room-temperature organic ferromagnetic semiconductors represent a promising frontier in developing next-generation electronic and spintronic devices.However,the origin of magnetic moments in organic ferromagnets and t...Room-temperature organic ferromagnetic semiconductors represent a promising frontier in developing next-generation electronic and spintronic devices.However,the origin of magnetic moments in organic ferromagnets and the acquisition of critical evidence for magnetic ordering remain incompletely understood.This study presents compelling evidence for room-temperature ferromagnetism in N,N′-diamino perylene bisimide(2NH2-PBI)radical aggregates through a comprehensive analysis utilizing X-ray magnetic circular dichroism(XMCD),low-field microwave absorption(LFMA)techniques and magnetic characterization.The 2NH2-PBI samples,prepared via hydrothermal reduction,exhibit a significant saturation magnetization of 0.8 emu g^(-1)(336.3 emumol−1)at 300 K,with a coercive field of 170 Oe.The XMCD measurements at the carbon K-edge exhibited a pronounced dichroic signal(~8.7%),confirming the origin of ferromagnetism in theπ-conjugated electrons of the perylene core.Density functional theory calculations further support this finding by demonstrating that spin density is primarily delocalized on theπ-conjugated skeleton,giving a microscopic explanation for the magnetic properties of 2NH2-PBI radicals.Furthermore,LFMA studies provide additional evidence of ferromagnetic ordering,showcasing hysteretic behavior consistent with domain wall dynamics.Our work indicates that imide-based radical molecules with extendedπ-conjugated structures constitute a class of effective magnetic functional units.展开更多
Hydrophilic dendrimers, especially poly（amidoamine）（PAMAM） dendrimers are widely applied in modifying fluorescent dyes to endow them with water solubility and biocompatibility for biologic fluorescence imaging.Com...Hydrophilic dendrimers, especially poly（amidoamine）（PAMAM） dendrimers are widely applied in modifying fluorescent dyes to endow them with water solubility and biocompatibility for biologic fluorescence imaging.Common preparation strategies of fluorescent dendrimers including encapsulating dyes or attaching dyes at periphery of dendrimers might cause uncertain constituent and lower biocompatibility. Here, we have developed a series of watersoluble fluorescent dendrimers with dye as core and fanshaped PAMAM as arms. Carboxylated perylene bisimides（PBI） dye and squarylium indocyanine（SICy） dye were conjugated with PAMAM dendrons by amidation to obtain a series of fluorescent dendrimers with enhanced water-solubility. Two PBI based dendrimers（PBI-G2.5 and PBI-G1.5）were chosen as model compounds for further optical, selfassembly and biological studies. In aqueous environment,PBI-G2.5 exhibited strong fluorescence, small size（~30 nm）and slightly positive surface charge（~2.46 mV）, which are ideal for biomedical applications. In vitro assays demonstrated that PBI-G2.5 nanoparticles accumulated in the cytoplasm of He La cells with rapid cellular uptake. The strong fluorescence in He La cells remained for over 48 h. To conclude, our study provides an effective strategy for preparing water-soluble fluorescent dendrimers towards long-term live cell imaging.展开更多
An isoindigo-based ＂double-cable＂ conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single-component polymer solar cells, in which a power conversion ...An isoindigo-based ＂double-cable＂ conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single-component polymer solar cells, in which a power conversion efficiency of 1% with broad photo-response from 300 nm to 800 nm was achieved. There is no evidence of large phase separation confirmed by AFM images and photoluminescence （PL） spectra. The space charge limit current measurements and light intensity dependence measurements indicate that the low electron mobility and the significant recombination of pho- togenerated charge carriers in active layer mainly account for the low performance of our solar cells. Our results suggest that these ＂double-cable＂ are oromising candidates for use in single-component polymer solar cells with NIR photoresponse.展开更多
Integrating multiple photosensitive properties into an“all-in-one”photosensitizer(PS)shows great promise for the treatment of cancers owing to synergistic effect among them.However,the development of such PSs,especi...Integrating multiple photosensitive properties into an“all-in-one”photosensitizer(PS)shows great promise for the treatment of cancers owing to synergistic effect among them.However,the development of such PSs,especially those that need a single laser source,remains a challenge.Herein,we report an orchestration of electron donors and acceptors in a propeller-like pentad,PBI-4Cz,where four carbazole(Cz)units are covalently linked to the ortho-positions of the perylene bisimide(PBI)core.Strong intramolecular donor-acceptor interaction significantly quenches the luminescence and largely extends the absorption spectra to near-infrared region.Excited-state dynamics investigated via femto-and nano-second transient absorption spectroscopy revealed exclusive charge separation of the PBI-4Cz within initial 0.5 ps when photoexcited regardless of which intermediate is involved.Energy dissipation of the resulting charge-separated state(PBI^(•−)-4Cz^(•−))is subjected to the toggle between intersystem-crossing toward excited triplet states and charge recombination toward ground states.Relative importance of the two pathways can be tuned by micro-environmental polarity,which endows PBI-4Cz remarkable performances of singlet-oxygen generation(>90.0%)in toluene and photothermal conversion(∼28.6%)in DMSO.Harnessing intrinsic photostability and excited-state processes of heavy-atom-free PBI derivatives not only holds a promise for multifunctional phototheranostics,but also provides a prototype for designing high-performance PSs with tunable photoconversion pathways.展开更多
Three "double-cable" conjugated polymers with thienopyrroledione-based backbone and perylene bisimide as side units were designed as electron acceptor for polymer-polymer solar cells. The polymers show broad...Three "double-cable" conjugated polymers with thienopyrroledione-based backbone and perylene bisimide as side units were designed as electron acceptor for polymer-polymer solar cells. The polymers show broad absorption spectra and low-lying frontier energy levels due to both aromatic backbone and side units. The new double-cable polymers can be used as electron acceptor to combine with several electron donors, in which power conversion efficiencies above 3% could be achieved.展开更多
We have fabricated a new perylene bisimide(PBI)folda-dimer(BPBI-CB-1)by tethering two PBI moieties to the ortho-carbon positions of a carborane unit.The synthesized compound adopted distinct configurations in differen...We have fabricated a new perylene bisimide(PBI)folda-dimer(BPBI-CB-1)by tethering two PBI moieties to the ortho-carbon positions of a carborane unit.The synthesized compound adopted distinct configurations in different solvents with dual emissions as its characteristic.The two PBI moieties in the molecule appeared either in a weakly interacted,monomer-like state or brought into close π-π contact with each other,forming an interacted stacking state.The equilibrium between these two states was governed by the nature of solvents and testing temperature.Spectroscopic and theoretical studies concluded that dual emission bands originated from intramolecular monomer-like and stacking states,respectively.Remarkably,in a solvent like 1,2-dichloroethane(DCE),both emission intensities increased with rising temperatures.The positive temperature response of the monomer emission was ascribed to an increased amount of monomer-like population,owing to its endothermic energy state,while the excimer emission was rationalized by increased population of the bright exciton state,resulting in an increased emission yield that compensated the diminished population of the stacking state.To our knowledge,this is the first report on positive temperature-responsive dual emissions associated with the synergism of intramolecular intersubunit aggregation/dissociation and excimer transformation.展开更多
Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of...Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of PBI anionic films. We unexpectedly discovered that pristine PBI dianion film showed p-type character, while oxidized dianion film(dominant neutral state with few radical anions) showed normal n-type semiconductor character based on Seebeck effect measurements. Both kinds of films exhibit high electrical conductivity with a potential for thermoelectric applications. The mechanism of polarity reversal is proposed.展开更多
Traditional photosensitizers are predominantly based on various types of polypyrrole macrocycles, which are generally used in homogeneous and/or suspension states. In the present study, a new non-polypyrrole-based pho...Traditional photosensitizers are predominantly based on various types of polypyrrole macrocycles, which are generally used in homogeneous and/or suspension states. In the present study, a new non-polypyrrole-based photosensitizer(LW-PBI) was developed via the introduction of a nonplanar spirofluorene into a derivative of perylene bisimides(PBI) containing two longalkyl chains. Photophysical studies demonstrated that the compound shows good solubility in common organic solvents, great photochemical stability, and high absorption efficiency in the visible light region. Due to containing of two energetically matchable, independent fluorescent units, the compound as prepared displays strong tendency to form non-fluorescent chargeseparated states under light irradiation in polar solvents. Based on the merits, LW-PBI was examined for its catalytic property in the photo-production of singlet oxygen in film state. Luckily, the compound is an effective photosensitizer in the generation of the active oxygen species as verified by its unique reaction with uric acid(UA). Further studies revealed that the effective photoproduction of singlet oxygen can be also realized via the utilization of a tiny and low-price LED lamp as a light source and as a film support. Detailed studies on the application of the conceptual device as a medical instrument for photodynamic therapy(PDT) are in progress.展开更多
文摘Supramolecular polymerization properties have been studied for a series of perylene bisimide(PBI)dyes containing identical hydrogen-bonding amide groups in imide positions but variable number or size of alkoxy substituents in bay-positions.
基金supported by the National Natural Science Foundation of China(NSFC)(51473009)the International Science&Technology Cooperation Program of China(2014DFA52820)
文摘Two perylene bisimides based non-fullerene small molecules, H-DIPBI and B-DIPBI, are applied into inverted planar heterojunction perovskite solar cells. The power conversion efficiency up to 11.6% has been achieved for device with B-DIPBI,indicating that non-fullerene acceptor can function as the electron transport layer to replace PCBM in perovskite solar cells.
基金Project(50573019)support by the National Natural Science Foundation of China
文摘An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoethyl）-piperazine. Then imidization of perylene-3, 4, 9, 10-tetracarboxylic acid dianhydride with 2,4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was carried out to afford a novel perylene derivative bearing two melamine blocks （S2） and 1, 6, 7, 12-tetra（4-tert-butyl phenoxy）-perylene-3, 4, 9, 10-tetracarboxylic acid bisimide （S1. The hydrogen-bonding interactions between S1 and S2 were investigated by IH NMR spectrum, UV/Vis spectrum and fluorescence spectrum. The influences on the morphologies of S1·S2 aggregates were investigated. The results show that well-defined nanofibers with a diameter of about 100 nm can be obtained by self-assembly between S1 and S2 only in CH2Cl2 solution. Based on these results, guidelines for the molecular design and self-assembly of supramolecular polymer materials are presented.
基金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financially supported by the Recruitment Program of Global Youth Experts of Chinathe National Natural Science Foundation of China(Nos.51603209 and 21574138)the Strategic Priority Research Program(No.XDB12030200)of the Chinese Academy of Sciences
文摘Perylene bisimide （PBI） unit has been widely used to design conjugated materials, which can be used as electron acceptor in organic solar ceils due to its strong electron-deficient ability. In this work, a conjugated polymer based on PBI dimer as monomer was designed, synthesized, and compared to the conjugated polymer containing single PBI as repeating units. The two conjugated polymers were found to have similar molecular weight, absorption spectra and energy levels. Density functional theory calculation revealed that the PBI dimer-based polymer exhibited highly twisted conjugated backbone due to the large dihedral angle between the two PBI units. The PBI-based polymers as electron acceptor were applied into polymer-polymer solar cells, in which PBI dimer-based polymer solar cells were found to show a high short circuit current density （Jsc = 11.2 mA.cm-2） and a high power conversion efficiency （PCE） of 4.5%. In comparison, the solar cells based on PBI-based polymer acceptor only provided a dsc of 7.2 mA.cm-2 and PCE of 2.5%. The significantly enhanced PCE in PBI dimer-based solar cells was attributed to the mixed phase in blended thin films, as revealed by atom force microscopy. This study demonstrates that PB! dimer can be used to design polymer acceptors for high performance polymer- polymer solar cells.
基金supported by the Recruitment Program of Global Youth Experts of Chinasupported by the National Natural Science Foundation of China(Nos. 21574138, 51603209 and 91633301)the Strategic Priority Research Program(No. XDB12030200) of the Chinese Academy of Sciences
文摘In this work, star-shaped perylene bisimide(PBI) derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies(PCEs) up to 4.27% due to the high short-circuit current density(Jsc) of 8.52 mA/cm^2 and fill factor(FF) of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.
基金This project is supported by the National Natural Science Foundation of China(No.20104001).
文摘N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4＇-difluorodiphenylsulfone and disodium 3,3＇-disulfonate4,4＇-difluorodiphenylsulfone gave ion-exchange sulfonated poly（ether sulfone）. The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.
文摘Designed and synthesized a new highly water soluble N,N^1-bis（2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethyl）-perylene -3,4,9,10-tetracarboxylic diimide from 2-（（5-（（dimethylamino）methyl）furan-2-yl）methylthio）ethanamine and perylene-3,4,9,10- tetracarboxylic dianhydride.The compound was characterized by ~1H,^（13）C,2D NMR,mass and IR techniques.The compound is highly fluorescent with good solubility in water and other polar solvents.
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Head-to-tail bonded perylene bisimide(PBI)dyads with different branched alkyl chains substituted at the terminal imide position show various stacking modes,which results in different effects on the excitonic processes and electron transportation.The dyad bearing branched alkyl chains with the branching sites close to the imide positions forms homogeneously amorphous state,while with branching sites being away from the imide positions the PBI core tend to stack with multiple modes.There are fewer energy trapping sites in the homogeneously amorphous state,but in the multiple stacking system the strongπ-πinteractions give more trapping sites.Our study demonstrates that the aggregation state of PBI-based acceptors plays an important role in the performances of organic solar cells(OSCs).Multiple stacking needs to be diminished to avoid the constrained exciton dissociation and retarded charge transport in the active layer.
基金supported by the Science and Technology Development Foundation of China Academy of Engineering Physics (Nos.2012A0302015,2012B0302050 and 2013B0302051)Doctoral Fund of Southwest University of Science and Technology (No.13zx7133)
文摘Fourfold benzocyclobutene-functionalized perylene bisimide（PBI 4） has been synthesized and its structure was characterized by FTIR,MS and NMR.PBI 4 can react either with itself,or the appropriate dienophiles to form the corresponding products under appropriate temperature.The polymer film obtained from the reaction of PBI 4 with methyl vinyl silicone rubber possessed excellent film forming properties including flatness.The optical properties of PBI 4 and polymer film obtained from the reaction of PBI 4 and methyl vinyl silicone rubber have been determined by UV/vis and fluorescence spectroscopy.
基金financially supported by the National Natural Science Foundation of China(No.21774107)the Jiangsu Government Scholarship for Overseas Studiesthe Initial Scientific Research Foundation of Yancheng Institute of Technology(No.KJC2014002)
文摘A novel perylene tetracarboxylic acid bisimide（PTCBI） in-chain polyethylene（PE） was first prepared via acyclic diene metathesis（ADMET） polymerization of PTCBI-functionalized α,ω-diene monomer. The polymers could spontaneously self-assemble into hollow cylindrical structures in which the π-π interaction between adjacent PTCBI moieties was enhanced and the electron mobility was possibly promoted. The hydrogenation of as-obtained polymer was readily accomplished, affording the desired precision PTCBI in-chain PE with a saturated backbone, which showed high glass transition temperature（Tg = 63 °C）, relatively wide range of light absorption（λ = 200-575 nm）, and higher LUMO level（-3.62 e V）. It can therefore serve as a superior model for facile construction of functional polyolefin and soluble PTCBI polymer with ordered architecture.
基金supported by the Natural Science Foundation of China(92463310 and 52203221)the open research fund of Songshan Lake Materials Laboratory(2023SLABFK05)+5 种基金National Key R&D Program of China(2020YFA0714604)Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates(2023B1212060003)Guangdong Provincial Quantum Science Strategic Initiative(GDZX2301002)Funding by Science and Technology Projects in Guangzhou(2024A04J2529)Young Talent Support Project of Guangzhou Association for Science and Technology(QT2024-001)the Fundamental Research Funds of State Key Laboratory of Luminescent Materials and Devices(No.Skllmd-2023-03 and Skllmd-2024-23).
文摘Room-temperature organic ferromagnetic semiconductors represent a promising frontier in developing next-generation electronic and spintronic devices.However,the origin of magnetic moments in organic ferromagnets and the acquisition of critical evidence for magnetic ordering remain incompletely understood.This study presents compelling evidence for room-temperature ferromagnetism in N,N′-diamino perylene bisimide(2NH2-PBI)radical aggregates through a comprehensive analysis utilizing X-ray magnetic circular dichroism(XMCD),low-field microwave absorption(LFMA)techniques and magnetic characterization.The 2NH2-PBI samples,prepared via hydrothermal reduction,exhibit a significant saturation magnetization of 0.8 emu g^(-1)(336.3 emumol−1)at 300 K,with a coercive field of 170 Oe.The XMCD measurements at the carbon K-edge exhibited a pronounced dichroic signal(~8.7%),confirming the origin of ferromagnetism in theπ-conjugated electrons of the perylene core.Density functional theory calculations further support this finding by demonstrating that spin density is primarily delocalized on theπ-conjugated skeleton,giving a microscopic explanation for the magnetic properties of 2NH2-PBI radicals.Furthermore,LFMA studies provide additional evidence of ferromagnetic ordering,showcasing hysteretic behavior consistent with domain wall dynamics.Our work indicates that imide-based radical molecules with extendedπ-conjugated structures constitute a class of effective magnetic functional units.
基金financially supported by the National Natural Science Foundation of China (21774007, 21574009 and 51521062)the Higher Education and High-quality and World-class Universities (PY201605)
文摘Hydrophilic dendrimers, especially poly（amidoamine）（PAMAM） dendrimers are widely applied in modifying fluorescent dyes to endow them with water solubility and biocompatibility for biologic fluorescence imaging.Common preparation strategies of fluorescent dendrimers including encapsulating dyes or attaching dyes at periphery of dendrimers might cause uncertain constituent and lower biocompatibility. Here, we have developed a series of watersoluble fluorescent dendrimers with dye as core and fanshaped PAMAM as arms. Carboxylated perylene bisimides（PBI） dye and squarylium indocyanine（SICy） dye were conjugated with PAMAM dendrons by amidation to obtain a series of fluorescent dendrimers with enhanced water-solubility. Two PBI based dendrimers（PBI-G2.5 and PBI-G1.5）were chosen as model compounds for further optical, selfassembly and biological studies. In aqueous environment,PBI-G2.5 exhibited strong fluorescence, small size（~30 nm）and slightly positive surface charge（~2.46 mV）, which are ideal for biomedical applications. In vitro assays demonstrated that PBI-G2.5 nanoparticles accumulated in the cytoplasm of He La cells with rapid cellular uptake. The strong fluorescence in He La cells remained for over 48 h. To conclude, our study provides an effective strategy for preparing water-soluble fluorescent dendrimers towards long-term live cell imaging.
文摘An isoindigo-based ＂double-cable＂ conjugated polymer bearing perylene bisimide side units was developed via Stille polymerization for application in single-component polymer solar cells, in which a power conversion efficiency of 1% with broad photo-response from 300 nm to 800 nm was achieved. There is no evidence of large phase separation confirmed by AFM images and photoluminescence （PL） spectra. The space charge limit current measurements and light intensity dependence measurements indicate that the low electron mobility and the significant recombination of pho- togenerated charge carriers in active layer mainly account for the low performance of our solar cells. Our results suggest that these ＂double-cable＂ are oromising candidates for use in single-component polymer solar cells with NIR photoresponse.
基金supported by the Natural Science Foundation of China(21820102005,22132002)111 project(B14041)+1 种基金the Fundamental Research Funds for the Central Universities of China(2019TS033,GK202001005 and GK202003034)the Youth Innovation Team of Shaanxi Universities。
文摘Integrating multiple photosensitive properties into an“all-in-one”photosensitizer(PS)shows great promise for the treatment of cancers owing to synergistic effect among them.However,the development of such PSs,especially those that need a single laser source,remains a challenge.Herein,we report an orchestration of electron donors and acceptors in a propeller-like pentad,PBI-4Cz,where four carbazole(Cz)units are covalently linked to the ortho-positions of the perylene bisimide(PBI)core.Strong intramolecular donor-acceptor interaction significantly quenches the luminescence and largely extends the absorption spectra to near-infrared region.Excited-state dynamics investigated via femto-and nano-second transient absorption spectroscopy revealed exclusive charge separation of the PBI-4Cz within initial 0.5 ps when photoexcited regardless of which intermediate is involved.Energy dissipation of the resulting charge-separated state(PBI^(•−)-4Cz^(•−))is subjected to the toggle between intersystem-crossing toward excited triplet states and charge recombination toward ground states.Relative importance of the two pathways can be tuned by micro-environmental polarity,which endows PBI-4Cz remarkable performances of singlet-oxygen generation(>90.0%)in toluene and photothermal conversion(∼28.6%)in DMSO.Harnessing intrinsic photostability and excited-state processes of heavy-atom-free PBI derivatives not only holds a promise for multifunctional phototheranostics,but also provides a prototype for designing high-performance PSs with tunable photoconversion pathways.
基金supported by the National Key R&D Program of China(2017YFA0204702)the National Natural Science Foundation of China(51773207,21574138,51603209,91633301)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12030200)Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry of Chinese Academy of Sciencesthe Recruitment Program of Global Youth Experts of Chinathe Director,Office of Science,Office of Basic Energy Sciences,of the US Department of Energy(DE-AC02-05CH11231)
文摘Three "double-cable" conjugated polymers with thienopyrroledione-based backbone and perylene bisimide as side units were designed as electron acceptor for polymer-polymer solar cells. The polymers show broad absorption spectra and low-lying frontier energy levels due to both aromatic backbone and side units. The new double-cable polymers can be used as electron acceptor to combine with several electron donors, in which power conversion efficiencies above 3% could be achieved.
基金the Natural Science Foundation of China(nos.21820102005,21527802,and 21673133)China 111 project(no.B14041)Program for Changjiang Scholars and Innovative Research Team in University(no.IRT-14R33).
文摘We have fabricated a new perylene bisimide(PBI)folda-dimer(BPBI-CB-1)by tethering two PBI moieties to the ortho-carbon positions of a carborane unit.The synthesized compound adopted distinct configurations in different solvents with dual emissions as its characteristic.The two PBI moieties in the molecule appeared either in a weakly interacted,monomer-like state or brought into close π-π contact with each other,forming an interacted stacking state.The equilibrium between these two states was governed by the nature of solvents and testing temperature.Spectroscopic and theoretical studies concluded that dual emission bands originated from intramolecular monomer-like and stacking states,respectively.Remarkably,in a solvent like 1,2-dichloroethane(DCE),both emission intensities increased with rising temperatures.The positive temperature response of the monomer emission was ascribed to an increased amount of monomer-like population,owing to its endothermic energy state,while the excimer emission was rationalized by increased population of the bright exciton state,resulting in an increased emission yield that compensated the diminished population of the stacking state.To our knowledge,this is the first report on positive temperature-responsive dual emissions associated with the synergism of intramolecular intersubunit aggregation/dissociation and excimer transformation.
基金supported by the National Natural Science Foundation of China (51573055, 51373054, 21334002, 51403063)National Basic Research Program of China (2014CB643504)+2 种基金Fundamental Research Funds for the Central UniversitiesChina Postdoctoral Science Fund (2014M562174)Introduced Innovative Research & Development Team of Guangdong (201101C0105067115)
文摘Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of PBI anionic films. We unexpectedly discovered that pristine PBI dianion film showed p-type character, while oxidized dianion film(dominant neutral state with few radical anions) showed normal n-type semiconductor character based on Seebeck effect measurements. Both kinds of films exhibit high electrical conductivity with a potential for thermoelectric applications. The mechanism of polarity reversal is proposed.
基金the National Natural Science Foundation of China(21527802,2167313,21820102005)111 Project(B14041)Program for Changjiang Scholars and Innovative Research Team in University(IRT-14R33)。
文摘Traditional photosensitizers are predominantly based on various types of polypyrrole macrocycles, which are generally used in homogeneous and/or suspension states. In the present study, a new non-polypyrrole-based photosensitizer(LW-PBI) was developed via the introduction of a nonplanar spirofluorene into a derivative of perylene bisimides(PBI) containing two longalkyl chains. Photophysical studies demonstrated that the compound shows good solubility in common organic solvents, great photochemical stability, and high absorption efficiency in the visible light region. Due to containing of two energetically matchable, independent fluorescent units, the compound as prepared displays strong tendency to form non-fluorescent chargeseparated states under light irradiation in polar solvents. Based on the merits, LW-PBI was examined for its catalytic property in the photo-production of singlet oxygen in film state. Luckily, the compound is an effective photosensitizer in the generation of the active oxygen species as verified by its unique reaction with uric acid(UA). Further studies revealed that the effective photoproduction of singlet oxygen can be also realized via the utilization of a tiny and low-price LED lamp as a light source and as a film support. Detailed studies on the application of the conceptual device as a medical instrument for photodynamic therapy(PDT) are in progress.
