ORGANIC & BIOMOLECULAR CHEMISTRY
·
2018
·Vol. 16
·期 31
·5598-5608
·
IF 3.423
Yaxiong Wei,Min Zheng,Qiaohui Zhou,Xiaoguo Zhou,Shilin Liu
A bodipy–C70 dyad was synthesized and applied in triplet–triplet annihilation (TTA) upconversion of perylene as a novel metal-free organic photosensitizer. The photophysical processes were investigated by the methods of steady-state UV-Vis absorption and fluorescence spectroscopy, nanosecond time-resolved transient absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The bodipy–C70 dyad showed an increased molar extinction coefficient up to 82 300 mol−1 cm−1 at 518 nm compared with the C70 monomer. With photo-excitation of the bodipy moiety at 532 nm, the intramolecular singlet–singlet energy transfer between bodipy and C70 units was efficient with a quantum yield of nearly 100%, and the lowest triplet state of the dyad was subsequently populated via ISC of the C70 moiety, with a lifetime of ca. 80 μs in toluene. Electrochemical investigation suggested that the intramolecular electron transfer of the excited dyad was thermodynamically prohibited in toluene due to the positive ΔGCS for charge-separation. With the presence of perylene in solution as the triplet energy acceptor and emitter, the TTA upconverted fluorescence was observed with a maximum quantum yield of 10.3%. The overall upconversion capability of 4417 M−1 cm−1 exceeded that of C70 approximately two-fold. Moreover, the bodipy–C70 dyad also exhibited an enhanced optical stability under intense irradiation. All data indicated that the dyad was another ideal photosensitizer for TTA upconversion of perylene in the fullerene derivative family.
研究领域:
材料科学
·
光化学
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DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Hui Niu,Huan Lin,Huiting Zhang,Longfeng Hu,Gangqiang Yu,Shuhong Wu,Jinlin Long,Quan-Fu An
Photocatalytic hydrogen evolution presents a sustainable method for clean energy generation, yet its efficiency remains limited by insufficient charge separation and transfer. Herein, we report a novel strategy to enhance photocatalytic efficiency by integrating both bulk and surface electric fields within self-assembled supramolecular photocatalyst. We synthesized perylene 3,4-dicarboxylic acid (PDA) with a large dipole moment and polar carboxyl groups, which self-assembles into ultrathin 2D nanosheets in water. The accumulation of dipole moments induces a bulk electric field, enabling ultrafast exciton dissociation into free charges. Concurrently, the exposed carboxyl groups generate a surface electric field, facilitating efficient charge extraction and transfer on the surface for proton reduction. The synergistic interplay between bulk and surface electric fields results in an impressive photocatalytic hydrogen production rate of 3.2 mmol g⁻¹ h⁻¹ , significantly surpassing that of the other perylene-based nanosheets relying solely on either bulk or surface electric fields. This study offers valuable insights into the distinct roles of bulk and surface electric fields in photocatalytic processes, and introduces a new design paradigm for photocatalysts to enhance solar-to-hydrogen conversion efficiency.
研究领域:
材料科学
·
能源科学
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DOI
高影响因子
TETRAHEDRON
·
2021
·
IF 2.457
Qin He,Fangdi Dong,Longjiang Xing,Huahong He,Xiaoping Chen,Huaqian Wang,Shaomin Ji,Yanping Huo
A series of perylene derivatives bearing electron-donating group (amino) and electron-withdrawing group (nitro, maleimide) at the 1- and 3-position have been synthesized. Interestingly, 3-monosubstituted perylenes shown different photophysical properties compared with 1-monosubstituted perylenes. 3-nitroperylene ( 3-NO ) attained 80.62% photoluminescence quantum yield ( Φ PL ) in toluene which is higher than 3-aminoperylene ( 3-NH , Φ PL = 71.70%) and 1-aminoperylene (1-NH, Φ PL = 48.04%), but for 1-nitroperylene ( 1-NO ), no fluorescence in any solvent were observed. The calculated ground-state geometries of 3-monosubstituted perylenes actually correspond to nearly planar structures, but the molecules substituted at the 1-position all have a twisted structure. Among them, 3-NO had a great π-conjugated system, resulting in the allowed ππ∗ fluorescence. In contrast, the twisting structure of 1-NO enhanced nonradiative decay pathways, coupled with the electron-withdrawing effect of the nitro group, which can explain the non-luminescence of 1-NO . Furthermore, the moleculars with maleimide group were used as “off-on” fluorescent probes and successfully used for imaging biothiols in living H1299 lung cancer cells. The fluorescence of probe 2 (substitutes at 3-position of perylene) afforded a 188-fold intensity increase after reaction with thiol which is much higher than (65-fold) probe 1 (substitutes at 1-position) because of the better π-conjugated structure. We envision that the investigation on the effects of substitute at 1-and 3-positions of perylene may be helpful for a rational design and application of highly fluorescent molecule base on perylene.
研究领域:
化学
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生物学
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医学
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DOI
高影响因子
JOURNAL OF LUMINESCENCE
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2017
·
IF 2.686
Mingguang Zhu,Youzhen Zhuo,Hongyu Guo,Fafu Yang,Jiabin Qiu
The first perylene liquid crystals bearing six peripheral alkyl substituents on both 1,6,7,12-bay positions and imides positions were designed and synthesized in yields of 72–77%. The studies on their mesomorphic behaviors suggested that they possessed good ordered hexagonal columnar mesophase with low phase transition temperatures and wide ranges of mesophase temperature in comparison with their precursors with chloric groups and the similar perylene liquid crystal with 4- tert -butylphenolic groups on bay positions. Their photophysical properties revealed that they also had higher fluorescence intensities and fluorescence quantum yields than that of their precursors with chloric groups and the similar perylene liquid crystal with 4- tert -butylphenolic groups on bay positions. The good fluorescence in both solution and solid film were observed for the first time for perylene liquid crystals. This research indicated that the introduction of long p -nonylphenol units on bay position is an effect strategy to obtain perylene liquid crystal with good liquid crystalline behavior and excellent fluorescent property.
研究领域:
材料科学
·
化学
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DOI
高影响因子
Journal of Materials Chemistry A
·
2015
·Vol. 3
·期 24
·12845-12851
·
IF 7.443
Ling Lin,Gui-Qi Gao,Qing Zhu,An-Wu Xu
Plasmon hot electron injection enhanced photocurrent has potential applications in light harvesting in photovoltaic devices. We demonstrate a cathodic photocurrent enhancement system utilizing strongly coupled Ag@perylene (Ag@Pe) core–shell nanowires, and the perylene shell thickness can be readily controlled. The strong coupling between the plasmonic resonance and molecular exciton resonance is evidenced by the substantial plasmon damping of Ag NWs and the enhancement of fluorescence of perylene with a red shift in Ag@Pe samples. The photocurrent of the Ag@Pe sample with a shell thickness of 5.8 nm (Ag@Pe-5.8 nm) shows a 16-fold enhancement compared to that of perylene. While, a simply mixed Ag–perylene sample displays only a 6-fold enhancement in photocurrent, indicating that the strong coupling in the Ag@Pe system plays a major role in the enhancement of photocurrent through hot electron transfer from the silver nanowires to perylene molecules. This strongly coupled Ag@Pe hetero-nanostructure could find potential applications in surface plasmon-driven, hot-electron solar cells and surface catalytic reactions.
研究领域:
材料科学
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光电子学
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DOI
高影响因子
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
·
2018
·
IF 1.217
Xiangfei Kong,Hongkang Gong,Shengping Dai,Wei Yao,Linping Mu,Shufen Zhang,Guixia Wang
Five novel dyads, consisting of a tetraphenylporphyrine unit connected to a perylene monoimide diester unit via a flexible bridge -CONH-(CH 2 ) n - (n = 4, 6, 8, 10 and 12), have been synthesized. Their structures were characterized by 13 C and 1 H nuclear magnetic resonance spectroscopy, infrared spectroscopy, mass spectrometry and elemental analysis. The UV-vis absorption spectra revealed these dyads have broad optical absorption in the ultraviolet and visible regions due to the complementary absorption of the two units. The differential scanning calorimetry traces and polarized optical microscopy textures showed all these dyads have columnar liquid crystal phases. Cyclic voltammetry revealed the highest occupied molecular orbitals of the dyads located on the porphyrin units, and the lowest unoccupied molecular orbitals located on the perylene units. In addition, these results were in agreement with that of the theoretical modeling. When excited at 423 or 473 nm, the photoluminescent emission spectra showed that the degree of fluorescence quenching of porphyrin units increased as the spacers became shorter. This quenching was ascribed to intramolecular photoinduced electron transfer, which also induced the dyad molecules to form the charge-separated states. The charge-separated molecules were further confirmed by the photocurrent response curves. These behaviors of broad absorption of the ultraviolet-visible light, yielding the charge-separated states of the molecules when excited and the formation of columnar liquid crystal phase made these dyads candidates for single-component photovoltaic active materials.
研究领域:
材料科学
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化学
·
光子学
✓ 已验证
DOI
高影响因子
Surfaces and Interfaces
·
2024
·
IF 5.7
Guangyu Wu,Guoyu Tai,Geng Li,Jiahuali Lu,Yuwei Pan,Jiangang Han,Weinan Xing
Perylene diimide (PDI) organic material and its derivatives as photocatalysts possesses excellent charge separation efficiency and are renowned as among the top n-type organic semiconductors capable of absorbing visible light owing to their narrow band gap (∼1.69 eV). Heterojunction photocatalysts with efficient electron transfer and excellent photocatalytic performance are of great significance for the degradation of organic compounds in the environment. In this work, a series of heterojunction catalysts (CNPDI) with robust interfacial charge transfer via π-π interaction were prepared using g-C 3 N 4 and different mass ratio of the self-assembled PDI as precursors, subsequently utilized as efficient visible-light-driven photocatalysts for the degradation of organic tetracycline. SEM and TEM results indicated that porous CN was completely wrapped around PDI nanorod structure formed by strong π-π interactions. In the presence of activating potassium peroxymonosulfate (PMS) substances, the kinetic rate constant of the CNPDI photocatalytic system clocked in at 0.026 min −1 , marking 2.36 fold increase compared to the original CN (0.011 min −1 ). The bolstered degradation performance was attributed to the built-in potential formed by the self-assembled PDI and CN, promoting the separation of electron-hole pairs and redistribution of charge density in the interface region. This work presents a useful insight into the crafting of PDI-based heterojunction photocatalysts for degradation environmental pharmaceutical pollutants.
研究领域:
环境科学
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材料科学
·
光催化
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2024
·
IF 5.3
Maoxin Zhang,Ruijuan Liao,Ao Zhang,Yi Fang,Xiaoli Song,Mingsi Xie,Chunxiu Zhang,Yuwen Feng,Haifeng Yu
A series of novel discotic liquid-crystalline donor–acceptor dyads (D-A) adjusted by changing the chain length of diester groups on perylene were synthesized based on triphenylene and perylene units which linked by a flexible linkage of 9-nonyloxy-1-amine. The mesomorphism properties and their self-assembly behaviors were studied by differential scanning calorimetry, polarized optical microscopy, one-dimensional wide-angle X-ray diffraction, small angle X-ray scattering and two-dimensional wide-angle X-ray diffraction. Charge carrier mobilities were measured by Time-of-flight device. These discotic liquid crystalline compounds exhibited highly efficient ambipolar charge-transport properties and the charge carrier mobility can reach the order of 10 −4 cm 2 v −1 s −1 by segregated donor–acceptor columns, providing potential utility of the strategy in organic optoelectronic applications.
研究领域:
材料科学
·
有机光电
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DOI
高影响因子
ANALYTICAL SCIENCES
·
2022
·Vol. 38
·期 7
·989-1002
·
IF 1.967
Zeng Qingli,Zhong Hui,Zhang Tianci,Huang Zhiqin,Li Laisheng
A large π-conjugated perylenediimide bridged bis (β-cyclodextrin)-bonded stationary phase (PBCDP) was first prepared and characterized. The chiral HPLC performance was systematically evaluated using a series of chiral probes. The results showed that PBCDP could resolve 36 kinds of chiral compounds in reversed-phase and polar organic modes with high resolutions ( R s) 1.48–3.28 for profens, 1.25–2.85 for triazoles, 1.34–5.29 for flavanones, 1.66–4.58 for amino acids and 1.22–1.97 for β-blockers. Especially, PBCDP could completely resolve acidic non-steroidal chiral drugs (profens) and simultaneously resolve basic five triazole pesticides, which were difficult to separate by ordinary CDCSP. Compared with CDCSP (15 kinds), the new stationary phase has a wider resolution range (36 kinds). Obviously, the synergistic inclusion of the two cavities of bridged cyclodextrin, as well as the large π–π stacking, hydrogen bond, dipole–dipole and basic primary amine site (–NH–) provided by the perylenediimide bridging group contributed together to the improvement of the above chiral separations. PBCDP was a new type of versatile chiral separation material without port derivatization. Graphical abstract
研究领域:
分析化学
·
色谱技术
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产品关联
DOI
PubMed
高影响因子
Materials
·
2020
·Vol. 13
·期 7
·1656
·
IF 3.057
Ying Wang,Xinguo Yang,Siyu Li,Tao Long,Wei Li
In this work, perylene bisimide derivatives (PBI-1 and PBI-2) with tertiary amine groups were designed and synthesized. To control the final morphologies and properties of their aggregates, seven kinds of organic acids were used to alter the self-assembly environment. The influence of organic acids on the morphology of the aggregates was investigated. Photophysical properties of the aggregates were markedly affected by the kind and concentration of the organic acid. The thermal and gas sensitivities of the PBI-1 aggregates were studied with the use of UV–visible spectroscopy and digital imaging. The shift of the UV–visible spectra varied with time, temperature, acid type and acid concentration. Furthermore, PBI-1 aggregates showed a red-to-blue color change after addition of seven organic acids, whereas the color of the PBI-2 aggregates remained red. These changes of morphologies, photophysical properties and their thermal and gas sensitivities make these aggregates potentially useful in the fields of optoelectronics or sensors.Keywords:perylene bisimide;self-assembly;organic acid;thermal sensitivity;gas sensitivity
研究领域:
材料科学
·
化学
✓ 已验证
DOI
PubMed
高影响因子
Royal Society Open Science
·
2018
·Vol. 5
·期 3
·
IF 2.504
Xiaoxiao Zhang,Tingyuan Gong,Hong Chi,Tianduo Li
Size control has been successfully achieved in inorganic materials, but it remains a challenge in polymer nanomaterials due to their polydispersity. Here, we report a facile approach to tailor the diameters of polyurethane (PU) nanoparticles (490 nm, 820 nm and 2.1 µm) via perylene bisimide (PBI) assisted self-assembly. The formed morphologies such as spindle, spherical and core–shell structures depend on the ratio of PBI and polymer concentrations. It is shown that the formation of PU nanoparticles is directed by π–π stacking of PBI and the morphology transition is not only affected by the amount of PBI incorporated, but also influenced by solvent, which controls the initial evaporation balance. Furthermore, the prepared PUs exhibit retained optical stability and enhanced thermal stability. The PUs, designed to have conjugated PBI segments in backbones, were synthesized via ring-opening and condensation reactions. Compared with the neat PU, gel permeation chromatography shows narrower molecular weight distribution. Fluorescence spectra and ultraviolet–visible spectra indicate retained maximum emission wavelength of PBI at 574 nm and 5.2% quantum yields. Thermo-gravimetric analysis and differential scanning calorimetry reveal 79°C higher decomposition temperature and 22°C higher glass transition temperature. This study provides a new way to fabricate well-defined nanostructures of functionalized PUs.
研究领域:
材料科学
·
高分子化学
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产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Yingying You,Haiguang Yuan,Yixiao Wu,Yiyang Ma,Chenchen Meng,Xuesong Zhao
Using solar energy to reduce bromate in drinking water is promising. Unfortunately, most effective photocatalysts for bromate conversion are metal-based semiconductors. Here, for the first time, metal-free hybrid composites made of red phosphorus and perylene diimide (RP/PDI) were successfully designed and constructed, and their excellent catalytic performance for removing bromate under visible light was demonstrated. Characterizations such as XRD, FTIR, Raman, SEM and XPS confirmed the successful preparation of the hybrid catalyst, and the impact of water matrices suggests that it can be used for the actual treatment of bromate. The bromate reduction rate of the prepared RP/PDI-2 was 4.2 times and 7.0 times faster than pure RP and PDI, respectively. As evidenced by EIS and EPR results, this improvement is mainly due to the formation of p-n heterojunctions , which enhanced the separation of charge carriers and inhibited the production of active species ( O 2 − and OH) with strong oxidative capabilities. Considered holistically, the current study provides not only a metal-free photocatalyst with good photoreduction performance, but also some guidance for the rational design of hybrid photocatalyst in the treatment of aqueous bromate.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）