Perylene Diimide Research Articles

Porphyrin photosensitizer molecules as effective medicine candidates for photodynamic therapy: electronic structure information aided design.

Traditional photosensitizers (PS) in photodynamic therapy (PDT) have restricted tissue penetrability of light and a lack of selectivity for tumor cells, which diminishes the efficiency of PDT. Our aim is to effectively screen porphyrin-based PS medication through computational simulations of large-scale design and screening of PDT candidates via a precise description of the state of the light-stimulated PS molecule. Perylene-diimide (PDI) shows an absorption band in the near-infrared region (NIR) and a great photostability. Meanwhile, the insertion of metal can enhance tumor targeting. Therefore, on the basis of the original porphyrin PS segments, a series of metalloporphyrin combined with PDI and additional allosteric Zn-porphyrin-PDI systems were designed and investigated. Geometrical structures, frontier molecular orbitals, ultraviolet-visible (UV-vis) absorption spectra, adiabatic electron affinities (AEA), especially the triplet excited states and spin-orbit coupling matrix elements (SOCME) of these expanded D-A porphyrin were studied in detail using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. PS candidates, conforming type I or II mechanism for PDT, have been researched carefully by molecular docking which targeted Factor-related apoptosis (Fas)/Fas ligand (Fasl) mediated signaling pathway. It was found that porphyrin-PDI, Fe2-porphyrin-PDI, Zn-porphyrin-PDI, Mg-porphyrin-PDI, Zn-porphyrin combined with PDI through single bond (compound 1), and two acetylenic bonds (compound 2) in this work would be proposed as potential PS candidates for PDT process. This study was expected to provide PS candidates for the development of novel medicines in PDT.

Dual-Modality Imaging with a Zwitterionic Fluorescent Probe for Reversible Monitoring of Mitochondrial Membrane Potential Dynamics.

Traditional fluorescence intensity-based probes face challenges in accurately measuring mitochondrial membrane potential (MMP) due to intramolecular fluorescence quenching. In this work, we introduce a novel approach by incorporating quenching moieties within the zwitterionic probe to eliminate self-quenching interference, thus, enabling real-time and precise visualization of reversible MMP changes. We synthesized a zwitterionic fluorescent probe consisting of silicon-rhodamine (SiR) that was hydroxyl-substituted on the bay position of perylene diimides (PDIs) connected via a polyethylene glycol (PEG) linker. The lipophilic cationic SiR facilitates the entry of the PDI into the mitochondria, where the alkaline pH environment (pH = 8.0) ionizes the hydroxyl to a negatively charged species, affecting the quenching efficiency of SiR depending on the distance between the PDI and SiR moieties regulated by the MMP. The rigid aromatic ring of the PDI and strong hydrophobic interactions with the lipid bilayer, along with the inhibitory effect of the negatively charged hydroxyl on internalization, ensure the retention of PDI within the mitochondria. As the MMP decreases, SiR shifts outward, reducing quenching by phenolic anions and restoring fluorescence. Conversely, as the MMP increases, SiR moves inward, intensifying quenching by phenolic ions and reducing fluorescence, enabling reversible visualization monitoring of the MMP. This strategy overcomes the limitations of traditional intensity-based probes, providing a new avenue for reversible monitoring of the MMP.

Perylene-Diimide-Based Supramolecular Radical Anion as a Platform for Highly Effective Photoreduction of Inert Sulfoxide to Sulfide.

Due to the limitations of common photoredox catalysts, unlocking their applications in photoreduction reactions remains an ongoing challenge. We herein present a supramolecular radical anion, PDI(CB[7])2, that formed by the assembly of perylene diimide derivative (PDI) and cucurbit[7]uril (CB[7]) via a host-guest interaction for an effective photoreduction reaction. Studies revealed that it could effectively accomplish a consecutive excitation process by two-photon excitation, enabling a potent photoreductant PDI(CB[7])2• - * that can even reduce the inert feedstocks, such as sulfoxides to sulfides. Mechanistic investigations indicate that, besides exceptional photophysical properties, supramolecular PDI(CB[7])2 also significantly enhances the lifetime and robustness of the in situ generated higher energy photoreductant PDI(CB[7])2• - * upon second quantum photon excitation, leading to the observed highly active photoreducing behavior.

Novel PDI-NH/PDI-COOH Supramolecular Junction for Enhanced Visible-Light Photocatalytic Phenol Degradation.

The development of efficient and environmentally friendly photocatalysts is crucial for addressing global energy and environmental challenges. Perylene diimide, an organic supramolecular material, holds great potential for applications in mineralized phenol. In this study, through the integration of different mass ratios of unmodified perylenimide (PDI-NH) into the self-assembly of amino acid-substituted perylenimide (PDI-COOH), a novel supramolecular organic heterojunction (PDICOOH/PDINH) was fabricated. The ensuing investigation focuses on its visible-light mineralized phenol properties. The results show that the optimal performance is observed with a composite mass fraction of 10%, leading to complete mineralization of 5 mg/L phenol within 5 h. The reaction exhibits one-stage kinetics with rate constants 13.80 and 1.30 times higher than those of PDI-NH and PDI-COOH, respectively. SEM and TEM reveal a heterogeneous interface between PDI-NH and PDI-COOH. Photoelectrochemical and Kelvin probe characterization confirm the generation of a built-in electric field at the interface, which is 1.73 times stronger than that of PDI-COOH. The introduction of PDI-NH promotes π-π stacking of PDI-COOH, while the built-in electric field facilitates efficient charge transfer at the interface, thereby enhancing phenol decomposition. The finding demonstrates that supramolecular heterojunctions have great potential as highly effective photocatalysts for environmental remediation applications.

Living Hybrid Exciton Materials: Enhanced Fluorescence and Chiroptical Properties in Living Supramolecular Polymers with Strong Frenkel/Charge‐Transfer Exciton Coupling

AbstractA family of chiral perylene diimides (PDIs) was newly developed as excellent circularly polarized luminescence (CPL) materials. They are asymmetrically derivatized with a double‐alkyl‐chained L‐ or D‐glutamate unit and a linear or branched alkyl chain. When water is added to the tetrahydrofuran (THF) solution of glutamate‐PDI‐linear‐alkyl chain compounds, kinetically formed H‐aggregates are formed in globular nanoparticles (NPs). These NPs undergo spontaneous transformation into thermodynamically stable nanotubes via helical nanostructures, which showed structured broad spectra originating from the strong coupling of delocalized Frenkel excitations (FE) and charge transfer excitations (CTE). Significant enhancement of circular dichroism (CD), fluorescence quantum yield, and circularly polarized luminescence (CPL) with luminescence dissymmetry factor (glum) are observed during the transformation of NPs to the FE/CTE‐coupled helical and tubular structures. This transformation process is significantly accelerated by applying physical stimuli, i.e., ultrasonication or adding helical aggregates as seed crystals, a feature unique to living supramolecular polymerization. Meanwhile, the branched chain‐containing PDIs only form H‐aggregates and did not show FE/CTE hybrid exciton states with living supramolecular polymerization properties. This study unveils that suitably designed chiral PDI derivatives show FE/CTE coupling accompanied by high fluorescence quantum yields, enhanced chiroptical properties, and supramolecular living polymerization characteristics.

Synergistically flexible-robust effects mediate the dynamic reconfiguration of perylene diimide polymer to enhance piezo-photocatalytic nitrate reduction

Identifying the spatial dynamic reconstruction of π-conjugated polymers for efficient carrier transport and controlling the intermediate process of the reaction are urgent and formidable challenges. In this study, a fresh perspective has emerged proposing to synergistically enhance the adaptability and resilience of dynamic torsion patterns in π-conjugated polymers to mediate charge separation and molecular activation. Excitingly, the highest flexible-robust structure and polarity of naphthalene-linked perylene diimide polymer (N-PDA) demonstrates a highest nitrate reduction rate of 5.36 mmol g−1 h−1 under light irradiation and ultrasonic condition, which is 7.5 times that of H-PDA. Theoretical calculations and experimental observations indicate that the strongest flexible-robust structure of N-PDA enhances the inclination of the rigid plane and atomic bond length, resulting in an accelerated uneven distribution of charges, molecular polarity, and electronic coupling to facilitate charge separation dynamics. Moreover, it exposes active sites that promote the adsorption and activation of NO3- ions while simultaneously regulating intermediate hydrogenation processes. Our study offers innovative prospects for enhancing catalytic efficiency through the implementation of spatial steric configuration of π-conjugated polymers.

Alkyl-Doping Enables Significant Suppression of Conformational Relaxation and Intermolecular Nonradiative Decay for Improved Near-Infrared Fluorescence Imaging.

Despite various efforts to optimize the near-infrared (NIR) performance of perylene diimide (PDI) derivatives for bio-imaging, convenient and efficient strategies to amplify the fluorescence of PDI derivatives in biological environment and the intrinsic mechanism studies are still lacking. Herein, we propose an alkyl-doping strategy to amplify the fluorescence of PDI derivative-based nanoparticles for improved NIR fluorescence imaging. The developed PDI derivative, OPE-PDI, shows much brighter in n-Hexane (HE) compared with that in other organic media, and the excited state dynamics investigation experimentally elucidates the solvent effect-induced suppression of intermolecular energy transfer and intramolecular nonradiative decay as the underlying mechanism for the fluorescence improvement. Theoretical calculations reveal the lowest reorganization energies of OPE-PDI in HE among various solvents, indicating the effectively suppressed conformational relaxation to support the strongest radiative decay. Inspired by this, an alkyl atmosphere mimicking HE is constructed by incorporating the octadecane into OPE-PDI-based nanoparticles, permitting up to 3-fold fluorescence improvement compared with the counterpart nanoparticles. Owing to the merits of high brightness, anti-photobleaching, and low biotoxicity for the optimal nanoparticles, they have been employed for probing and long-term monitoring of tumor. This work highlights a facile strategy for the fluorescence enhancement of PDI derivative-based nanoparticles.

Living Hybrid Exciton Materials: Enhanced Fluorescence and Chiroptical Properties in Living Supramolecular Polymers with Strong Frenkel/Charge-Transfer Exciton Coupling.

A family of chiral perylene diimides (PDIs) was newly developed as excellent circularly polarized luminescence (CPL) materials. They are asymmetrically derivatized with a double-alkyl-chained L- or D-glutamate unit and a linear or branched alkyl chain. When water is added to the tetrahydrofuran (THF) solution of glutamate-PDI-linear-alkyl chain compounds, kinetically formed H-aggregates are formed in globular nanoparticles (NPs). These NPs undergo spontaneous transformation into thermodynamically stable nanotubes via helical nanostructures, which showed structured broad spectra originating from the strong coupling of delocalized Frenkel excitations (FE) and charge transfer excitations (CTE). Significant enhancement of circular dichroism (CD), fluorescence quantum yield, and circularly polarized luminescence (CPL) with luminescence dissymmetry factor (glum) are observed during the transformation of NPs to the FE/CTE-coupled helical and tubular structures. This transformation process is significantly accelerated by applying physical stimuli, i.e., ultrasonication or adding helical aggregates as seed crystals, a feature unique to living supramolecular polymerization. Meanwhile, the branched chain-containing PDIs only form H-aggregates and did not show FE/CTE hybrid exciton states with living supramolecular polymerization properties. This study unveils that suitably designed chiral PDI derivatives show FE/CTE coupling accompanied by high fluorescence quantum yields, enhanced chiroptical properties, and supramolecular living polymerization characteristics.

A morphologically transformable hypoxia-induced radical anion for tumor-specific photothermal therapy

Tumor microenvironment activatable therapeutic agents and their effective tumor accumulation are significant for selective tumor treatment. Herein, we provide an unadulterated nanomaterial combining the above advantages. We synthesize a perylene diimide (PDI) molecule substituted by glutamic acid (Glu), which can self-assemble into small spherical nanoparticles (PDI-SG) in aqueous solution. PDI-SG can not only be transformed into nanofibers at low pH conditions but also be reduced to PDI radical anion (PDI·‒), which exhibits strong near-infrared absorption and excellent photothermal performance. More importantly, PDI-SG can also be reduced to PDI·‒ in hypoxic tumors to ablate the tumors and minimize the damage to normal tissues. The morphological transformation from small nanoparticles to nanofibers makes for better tumor accumulation and retention. This work sheds light on the design of tumor microenvironment activatable therapeutics with precise structures for high-performance tumor therapy.

Synthesis and characterization of new perylenediimide derivatives: Promising low-cost electron transport materials for perovskite solar cells

In organic-inorganic perovskite solar cells (PSCs), the electron transport layer (ETL) plays a crucial role providing efficient electron extraction and transport required for achieving high device performance. Compared to traditional fullerene-based electron-transport materials (ETMs), non-fullerene small molecules have attracted much attention due to their tunable optoelectronic properties, lower cost, and much higher stability. In this work, we synthesized and characterized four perylenediimide (PDI) derivatives and investigated their optoelectronic properties in the context of application as ETMs for PSCs. To establish the compatibility of PDI films with perovskite absorber material, the surface properties of Cs0.12FA0.88PbI3/PDI bilayer stacks were studied using contact angle and infrared scattering scanning near-field microscopy methods. A study of the photochemical stability of these bilayer stacks showed that coating the perovskite film with a layer of PDI improves its tolerance with respect to light. Utilizing these molecules as ETMs in the inverted p-i-n PSCs delivered light power conversion efficiencies ranging from 11.1 % to 15.4 %, thus indicating the considerable effect of the PDI derivative molecular structure on the photovoltaic properties. Further development of this research direction may lead to the rational design of advanced PDI-based electron transport materials for efficient and stable PSCs.

Design, synthesis, solvatochromism, and colorimetric detection of amines based on isolated perylene bisimide anionic radical π-dimers

Some π-molecular radicals typically exist in solution as π-dimers with metastable characteristics. Therefore, attempting to improve the stability of radical π-dimers is a fascinating endeavor. Herein, a series of hydroxyl-functionalised isolated perylene bisimide anionic radical π-dimers were obtained by using intramolecular hydrogen bond assistance in a one-step process for the first time. It is also found that these radical π-dimers exhibit solvatochromism and acid-base discoloration, when the intermolecular hydrogen bonds are disrupted. Perylene bisimide anionic radical π-dimers exhibit unique properties such as solvatochromism and acid-base discoloration. These characteristics make them suitable for ultra-sensitive colorimetric and fluorescent dual-signal detection of amines. Among them the π-dimer 3 achievable the lowest detection limits of 0.13 ppb, 0.02 ppb and 0.049 ppb for primary, secondary and tertiary amines, respectively. Additionally, colorimetric films prepared using these radical π-dimers demonstrate high sensitivity, enabling detection of amines at ppb levels. We believe that this class of radical π-dimers could be develop into a new class of environmental stimuli-responsive materials.

Correction to “A Comprehensive Analysis of Electronic Transitions in Naphthalene and Perylene Diimide Derivatives Through Computational Methods”

Correction to “A Comprehensive Analysis of Electronic Transitions in Naphthalene and Perylene Diimide Derivatives Through Computational Methods”

Self-assembled perylene diimide decorated g-C3N4 heterojunction catalyst with strong interfacial charge transfer through π-π interaction for efficient boosted photocatalytic degradation of tetracycline

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-C3N4 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.

Long wavelength near-infrared and red light-driven consecutive photo-induced electron transfer for highly effective photoredox catalysis

Consecutive photoinduced electron transfer (conPET) processes accumulate the energies of two photons to overcome the thermodynamic limit of traditional photoredox catalysis. However, the excitation wavelength of conPET systems mainly focused on short wavelength visible light, leading to photodamage and incompatibility with large-scale reactions. Herein, we report on conPET systems triggered by near-infrared (NIR) and red light. Specifically, a blue-absorbing conPET photocatalyst, perylene diimide (PDI) is sensitized by a palladium-based photosensitizer to triplet excited state (3PDI*), which generates PDI radical anion (PDI•–) over 100-fold faster than that in the conventional conPET. Accordingly, photoreduction with superior reaction rate and penetration depth, as well as reduced photodamage is detected. More importantly, our work offers comprehensive design rules for the triplet-mediated conPET strategy, whose versatility is confirmed by metal-free dye pairs and NIR-active PtTNP/PDI. Notably, our work achieves NIR-driven atom transfer radical polymerization using an inert aromatic halide as the initiator.

Visible light activation of persulfate by α-Fe2O3/PDINH photocatalyst for sulfamethoxazole degradation

Self-made α-Fe2O3 and commercially perylene diimide (PDINH) were selected to prepare α-Fe2O3/PDINH composite photocatalysts (FPx, where x represents the mass percentage of PDINH), and these were utilized for the activation of peroxydisulfate (PDS) to degrade sulfamethoxazole (SMX) in water under visible light. The FP3/PDS/vis system was able to remove about 98.9 % of SMX in 140 min, and the corresponding reaction rate reached 0.0327 min−1, for 23.4 and 18.2 times greater than α-Fe2O3/PDS/vis system and the PDINH/PDS/vis system, respectively. PDS played a major role in SMX degrading and both free radical (SO4−, OH, O2−) and non-free radical (1O2, h+) were involved in the removal of SMX. Interestingly, with the exception of h+, all radicals and non-radicals were directly or indirectly derived from PDS activation rather than photocatalysis. Besides, 3 degradation pathways and 13 by-products of SMX were identified, and the toxicity analyses of the intermediates demonstrated that the FPx/PDS/vis system could effectively remove SMX from water and reduce its biotoxicity. This work offers insights into the photocatalytic activation of PDS for removing SMX from water.

Stability assessment of PTB7‐Th and a quinoxaline‐based polymer in both organic thin film transistors and in organic photovoltaic devices

AbstractHerein, we perform a stability assessment of two conjugated polymers that are conventionally used as electron donor polymers in the active layer of organic photovoltaic (OPV). More specifically, the impact of thermal annealing, a post‐treatment commonly applied in the OPV community, is evaluated in terms of device performance and stability. The two polymers are PTB7‐Th and QX1, and they are respectively blended with a non‐fullerene electron acceptor, herein a derivative of N‐annulated perylene diimide, that is, tPDI2N‐EH. These blends are targeted for their relatively high power conversion efficiency in outdoor conditions, but also for their potential as efficient active layer in low‐intensity (indoor) conditions—while these blends have been reported, no study on the impact of thermal annealing on their stability has been performed yet. The performance stability of these devices, tracked via the open circuit voltage, the short‐circuit current, the fill factor, and the power conversion efficiency metrics, were evaluated each day for 2 weeks and correlated to an evaluation of the microstructure of the active layer, evaluated using atomic force microscopy and UV–visible absorbance spectroscopy. Finally, transistors were prepared using only the two electron donor polymers, PTB7‐Th and QX1, to assess if some correlations could be made between the behaviour of the OPV devices and that of the electronic charge mobilities. Results contribute to identify which molecular structures and which post‐treatments are ideal to promote the stability of the active layers in the context of OPV devices.

Dual-Mode Immunoassay Constructed by Water-Induced Perylene Diimide Supramolecular Self-Assembly and Enzymatic Biocatalytic Precipitation Strategy.

A water-induced electron-deficient dye, the supramolecule perylene diimide (PDI), has been identified recently. PDI possesses advantages such as easy reduction, nontoxicity, low cost, and simple preparation, making it a promising candidate for electrochemiluminescence (ECL) sensing platforms. In this study, a series of PDI supramolecular systems with morphological changes were prepared by utilizing water molecules to induce PDI self-assembly. This method improves the π-π stacking interactions between PDI molecules and effectively mitigates the aggregation-caused quenching (ACQ) effect on the luminous efficiency of the coplanar polycyclic aromatic hydrocarbon PDI. It is noteworthy that excellent ECL emission performance of the PDI supramolecular system was observed at -0.4 V. This low excitation potential aids in preserving antigen-antibody bioactivity and ensures accurate identification of the immune response. As a proof of concept, a dual-mode immunosensing platform for carcinoembryonic antigen (CEA) detection was constructed using an enzymatic biocatalytic precipitation (EBCP) strategy. The dual-mode immunosensor exhibited good detection performance in the concentration range of 0.001-80 ng·mL-1, presenting an advanced bioprotective analytical method for CEA detection.

Direct arylation-derived non-ionic star-shaped oligomeric CIL materials with Dramatically reduced work functions for organic solar cells

Although numerous photoactive layer materials have been explored for organic solar cells (OSCs), the cathode interface layer (CIL) materials still largely lag behind, however. Till now, ionic perylene diimide (PDI) derivatives are one of the most representative conjugated small molecules CIL materials for OSC. In this study, three new non-ionic star-shaped oligomeric CIL materials named W1, W2 and W3 involving 1,3,5-tribromo-2,4,6-trifluoro-benzene building, cyclopentadithiophene, rhodamine and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile blocks were designed and facilely synthesized via atom-economic direct C–H arylation for OSC. In the follow-up study of structure-property correlation, it was found that all three molecules possess the deepened work function (WF). W1-3 show good electron transport, and are introduced into the PM6:Y6 system to further explore its effect as CIL that, can effectively suppress charge recombination. Among them, W1 has the best effect of reducing the WF, which reduces the WF of the Ag electrode from 4.30 eV to 3.41 eV. Owing to its deepest WF and best alcoholic processability. The W1-based devices achieve a highest-power conversion efficiency (PCE) of 14.53 %, corresponding to a VOC of 0.85 V, a JSC of 25.17 mA cm−2, and an FF of 67.21 %. Our work opens up a new direction for non-ionic, non-PDI and non-fused ring star-shaped CIL materials, and thus diversify the CIL materials.

Revelation of room temperature liquid crystallinity and yellow-orange electroluminescence (EQE>7%) in a columnar self-assembled N-annulated perylene bisimide

The synthesis of highly fluorescent compounds is a critical necessity to facilitate cost-effective and metal-independent production of organic light-emitting diodes (OLEDs). This investigation introduces a readily soluble, electron-deficient N-annulated perylene bisimide (PBI-NST) equipped with a swallow tail, exhibiting room temperature columnar oblique mesophase with a low clearing point and high photoluminescence quantum yield, positioning it as a promising candidate for efficient OLEDs. Leveraging the luminescent properties of PBI-NST, a series of OLED devices were fabricated with PBI-NST as the sole emitter and at various concentrations in CBP host material. Impressively, doped devices employing the compound at 0.5 wt% emitter within the host material CBP displayed an exceptional external quantum efficiency (EQE) of 7.2 %, accompanied by a luminance of 2689 cd/m2. Further, a voltage dependent emission tuning was also noticed. The notable increase in EQE is mainly attributed to the contributions of hybrid local and charge transfer (HLCT) and triplet–triplet annihilation (TTA) process. The substantial enhancement in EQE marks a significant advancement in the application of multifunctional columnar self-assembled materials for OLED development.

Aerobic Oxidative Synthesis of N‐Containing Heterocycles from o‐Substituted Aniline Derivatives and Primary Amines by Perylene Diimide Catalysis

The commercially available 3,4,9,10‐perylenetetracarboxylic diimide (PTCDI) acted as a heterogeneous catalyst to catalyze aerobic oxidative synthesis of benzimidazoles, benzothiazoles, and quinoxalines from o‐substituted aniline derivatives and primary amines in high yields with oxygen as the terminal oxidant. The gram scale reaction and reusability (up to six cycles) of the PTCDI catalyst were also successful and would greatly benefit industrial applications.