Diimide Derivatives Research Articles

A metal-organic framework with mixed electron donor and electron acceptor ligands for efficient lithium-ion storage.

Electron donor tetrathiafulvalene (TTF) and electron acceptor naphthalene diimide (NDI) derivatives were used to synthesize a 3D Zn-TTF/NDI-MOF. Multiple redox active sites and charge transfer endow the pristine MOF anode with excellent rate behavior and long term cycling performance (with an average specific capacity of 956 mA h g-1 at 1 A g-1 over 600 cycles). This study highlights the great potential of elaborately-designed MOFs for developing efficient anode materials.

Hypoxia-Initiated Supramolecular Free Radicals Induce Intracellular Polymerization for Precision Tumor Therapy.

Despite the development of various controlled release systems for antitumor therapies, off-target side effects remain a persistent challenge. In situ therapeutic synthesis from biocompatible substances offers a safer and more precise alternative. This study presents a hypoxia-initiated supramolecular free radical system capable of inducing intracellular polymerization, thereby disrupting the cytoskeleton and organelles within 4T1 cells. The system utilizes a 2:1 supramolecular host-guest complex of cucurbit[7]uril (CB[7]) and perylene diimide derivative (PDI), termed PDI+2CB[7], which is selectively reduced by the tumor's hypoxic and reducing environment to generate delocalized free radical anions. CB[7] effectively stabilizes these anions, enabling the PDI+2CB[7] complex to initiate free radical polymerization with 2-hydroxyethyl methacrylate (HEMA) inside the 4T1 cells. The resulting in situ polymerization significantly disrupts tumor metabolism, leading to a strong antitumor response without systemic toxicity. This study demonstrates that stable, endogenous stimulus-induced supramolecular free radicals can trigger intracellular polymerization reactions, achieving a selective and effective antitumor therapy without conventional chemotherapeutic agents.

Novel Electrochemiluminescence Sensor for Dopamine Detection Based on Perylene Diimide/CuO Nanomaterials.

Dopamine (DA) is an important catecholamine neurotransmitter and its abnormal concentration is closely related to diseases such as hypertension, Parkinson's disease and schizophrenia. Due to the advantages of high sensitivity and fast response for electrochemiluminescence (ECL), developing ECL sensors for detecting DA was very critical in clinical diagnosis. ECL resonance energy transfer (ECL-RET) was an effective signaling mechanism. However, the shortage of highly efficient ECL-RET pairs impeded the development of DA sensors. Herein, methyl-modified perylene diimide derivative (PDI-CH3) self-assembly nanorod materials as luminophores and CuO nanomaterials as acceptors were integrated into nanocomposites. An obvious ECL-RET was found in PDI-CH3/CuO nanocomposites. After PDI-CH3/CuO nanocomposites were treated with DA, a large increase in ECL intensity was observed. Then, PDI-CH3/CuO nanocomposites were taken as an ECL platform to detect DA. This ECL sensor exhibited a linear response to DA from 10-12 M to 10-8 M with a limit of detection of 0.20 pM. Compared with other sensors for DA detection, the constructed ECL sensor exhibited higher sensitivity. In addition, the novel ECL sensor in this work showed good practicability in a human serum sample.

A Crystalline 3D Supramolecular Polymer Constructed by Clamparene-Based Controllable Self-Assembly and Its Application in Photothermal Conversion.

The development of well-defined three-dimensional supramolecular polymers presents significant challenges, particularly in achieving crystalline state structures. This study addresses this challenge by presenting the construction of a crystalline three-dimensional supramolecular polymer through the self-assembly of clamparene (CLP) and a naphthalene diimide derivative (NDIOH) in the solid state. The hierarchical self-assembly progresses from one-dimensional linear supramolecular polymers to two-dimensional supramolecular polymers and ultimately to a crystalline three-dimensional supramolecular polymer. Moreover, the prepared crystalline three-dimensional supramolecular polymer demonstrates effective photothermal conversion. This work advances the understanding and design of functional three-dimensional supramolecular polymers in the crystalline state.

Conformation Regulation of Perylene Diimide Derivatives by Lanthanide Coordination for Turn-On Fluorescence Sensing of Sarin Simulants.

Fluorescent metal-organic frameworks (MOFs) are promising sensing materials that have received much attention in recent years, in which the organic ligand conformation changes usually lead to variations of their sensing behavior. Based on this, in the present work, perylene diimide (PDI) derivatives with excellent photochemical properties closely related to their conformation and molecule packing fashion were selected as organic linkers to detect sarin simulant diethyl chlorophosphate (DCP). By the coordination interactions with large lanthanide cations through terminal carboxylate groups from the PDI derivative, a series of one-dimensional coordination polymers, named [Ln(PDICl4-2COO)(μ2-O)0.5(DMF)1.5] (SNNU-112, Ln = Yb/Tb/Sm/Nd/Pr/Gd/Eu/Er/Ce, PDICl4-2COOH = N,N'-bis(4-benzoic acid)-1,2,6,7-tetrachlorohydrazone-3,4,9,10-tetracarboxylic acid diimide) were synthesized. Regulated by the coordination process, the ligand undergoes a certain degree of conformational turnover and thus leads to an electron distribution change compared to free PDICl4-2COOH. Notably, the contact with the DCP molecule triggered a further ligand conformational conversion of PDI ligands in SNNU-112 and thus caused a fluorescence turn-on phenomenon realizing a well-defined fluorescence detection performance for DCP on the basis of a photoinduced electron transfer process. Among nine lanthanide MOFs, Yb-MOF sensor exhibited the lowest detection limit (4.36 ppb), fast response, high selectivity, and good recyclability. Such molecular conformation regulation of PDI derivatives by metal coordination may provide a new way for the exploration of fluorescent sensors.

Ligand Triplet Energy Transfer from Perylene Diimide Derivatives to PbS Quantum Dots in Solution

Ligand Triplet Energy Transfer from Perylene Diimide Derivatives to PbS Quantum Dots in Solution

19.5%‐Efficiency Organic Solar Cells with High Thickness Tolerance and Exceptional Device Stability Enabled by TEMPO‐Functionalized Perylene Diimide as a Cathode Interface Layer

AbstractThe cathode interface material is pivotal for achieving excellent photovoltaic performance and device stability in organic solar cells (OSCs). However, currently, few interface materials can simultaneously satisfy multiple criteria such as low cost, high efficiency, insensitivity to film thickness, and good stability. To address this challenge, a novel perylene diimide (PDI) derivative, P‐C3T is designed and synthesized, by incorporating stable free radical unit TEMPO and polar quaternary ammonium salt as side chains. P‐C3T is facile to synthesize and cost‐effective, while also exhibiting good conductivity and excellent ohmic contact characteristics in OSCs. When utilized as the cathode interface material, the device based on D18:L8‐BO achieves a remarkable power conversion efficiency (PCE) of 19.52%, which is one of the highest levels reported for binary single‐junction OSCs. Notably, devices based on P‐C3T exhibit remarkable insensitivity to film thickness, with the PCE remaining at 95% of the initial efficiency even at a thickness of 40 nm. Furthermore, P‐C3T‐based OSCs demonstrate exceptional storage stability and improved light stability. In summary, with its high PCE, excellent thickness insensitivity, and good stability, P‐C3T is anticipated to be a promising candidate material for large‐area roll‐to‐roll processing of OSCs.

Emissive Features of Perylene Diimide Derivative with β-Cyclodextrin: Probing the role of inter and intramolecular interactions.

Perylene diimide (PDI) derivatives have been extensively explored as chromophoric dyes for functional organic materials. Here, the custom synthesized tyrosine appended perylene diimide (PDI-Tyr) derivative has shown strong aggregation in aqueous medium diminishing its emissive features, which was surpassed by the supramolecular interaction with β-cyclodextrin (β-CD). Complex formation between PDI-Tyr and β-CD, proposed from the absorption and emission studies, have been substantiated by the 1H-NMR, ITC and geometry optimization data. Time-resolved emission and transient absorption studies carried out on PDI-Tyr in the absence and presence of β-CD, revealed an excited state intramolecular charge transfer (ICT) process from the tyrosine moiety to the PDI core with a time constant of ~30 ps, and the same gets retarded on encapsulation of the tyrosine groups in the βCD:PDI-Tyr (2:1) complex and the kinetics slows down to ~480ps, reviving the emissive features. The absence of a long lifetime component and the lower emission enhancement in the monomeric condition as compared to the phenyl alanine (PDI-Phe) derivative, emphasizes the major role of the ICT process in PDI-Tyr, which subdue the features of intermolecular aggregation, establishing the tunability of the emissive properties with the customization of intra and intermolecular interactions.

Front Cover: Investigations of Crucial Factors for the Non‐Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets (Chem. Eur. J. 67/2024)

Front Cover: Investigations of Crucial Factors for the Non‐Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets (Chem. Eur. J. 67/2024)

Supercapacitor performance evaluation with changes of microstructure in carbon electrode from perylene diimide derivative

Structural regulation of carbon electrode materials is an effective route to reinforce the performance of supercapacitors. Due to its high carbon content and easy gelation, perylene diimide derivative (PDI-d) is a good precursor for preparation of microstructure-controlled carbons. Here, PDI-d is synthesized and its gels are prepared under the action of glucono delta lactone (GDL). The PDI-d gels are subjected to freezing in liquid nitrogen or refrigerator, freeze-drying, carbonization for harvest of derived carbons with different structures and element doping. The derived carbons through liquid nitrogen freezing present fiber-woven three-dimensional connected porous structures, while those subjected to freezing in refrigerators are lamellar structures. N and Sn can be doped in the carbons using triethylamine (TEA) and K2SnO3·3H2O as solvents for PDI-d dissolution, respectively. The carbons with connected pores show higher specific surface area (454 m2 g−1), and better electrochemical performance than the carbons with lamellar structures. The optimum specific capacitance (200.1 F g−1) can be acquired in 3D porous carbons. The incorporation of N and Sn can further optimize the electrochemical performance. Specially, the Sn-doped porous structure derived carbon achieves a large energy density (27.79 Wh kg−1) and keeps good cycle stability (94.7 % after 10,000 cycles).

Investigations of Crucial Factors for the Non-Covalent Functionalization of Black Phosphorus (BP) using Perylene Diimide Derivatives for the Passivation of BP Nanosheets.

The non-covalent functionalization of black phosphorus (BP) was studied with a scope of ten tailor-made perylene diimides (PDIs). A combination of UV/Vis-, fluorescence-, as well as Raman spectroscopy and atomic force microscopy was used to investigate the structural factors, which contribute to a pronounced PDI-BP interaction and thus support the protection of BP nanosheets against oxidative degradation. We were able to show, that water-soluble, amphiphilic PDIs with highly charged head groups can be used for the non-covalent functionalization of BP in aqueous media. Here, based on the hydrophobic effect, an efficient adsorption of the respective PDI molecules takes place and leads to the formation of a passivating film, yielding a considerable stabilization of the BP flakes under ambient conditions exceeding 30 days.

MAPLE-Deposited Perylene Diimide Derivative Based Layers for Optoelectronic Applications.

Nowadays, the development of devices based on organic materials is an interesting research challenge. The performance of such devices is strongly influenced by material selection, material properties, design, and the manufacturing process. Usually, buckminsterfullerene (C60) is employed as electron transport material in organic photovoltaic (OPV) devices due to its high mobility. However, considering its low solubility, there have been many attempts to replace it with more soluble non-fullerene compounds. In this study, bulk heterojunction thin films with various compositions of zinc phthalocyanine (ZnPc), a perylene diimide derivative, or C60 were prepared by matrix-assisted pulsed laser evaporation (MAPLE) technique to assess the influence of C60 replacement on fabricated heterostructure properties. The investigations revealed that the optical features and the electrical parameters of the organic heterostructures based on this perylene diimide derivative used as an organic acceptor were improved. An increase in the JSC value (4.3 × 10-4 A/cm2) was obtained for the structures where the perylene diimide derivative acceptor entirely replaced C60 compared to the JSC value (7.5 × 10-8 A/cm2) for the heterostructure fabricated only with fullerene. These results are encouraging, demonstrating the potential of non-fullerene compounds as electron transport material in OPV devices.

Controlled Photooxidation via Singlet Oxygen Generation by Triplet Harvesting in a Heavy Atom Free Pure Organic Dithienylethene-Naphthalene Diimide.

Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal-free pure organic emitters, connected with a photoswitch, capable of generating "on-demand" 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline-dithienylethene (DTE)-core-substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline-DTE-cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ~0.55 in DCM and 0.73 in methanol). The designed molecule exhibits a long-lived emission (τ∼1.1 μs) and very small singlet-triplet splitting (ΔEST) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time-resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited-state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.

Non-linear optical properties of hybrid materials of (OLi3) superalkali doped perylene diimide (PDI) derivative: comprehensively study via silico-technique

PDI-Imidazole and PDI-Imidazole combined with OLi3 (OLi3@PDI-Imidazole) were the two types of materials that we examined in this study to see how light behaved in each of the complex. To explore this, we employed the three different method such as rB3LYP/6–31G(d, p) DFT, CAM-B3LYP and WB97XD. The impact of PDI-Imidazole and OLi3@PDI-Imidazole geometries, maximum absorption ( λmax ), FMO, vertical ionization energies ( EVI ), Binding Energies ( Eb ), Hyperpolarizabilities, DOS, Dipole Moments (μ), ESP, EDDM, and Global Reactivity parameters have been examined. The type of contacts as well as the vibrational frequencies of PDI-Imidazole and OLi3@PDI-Imidazole were investigated using NCl, iso-surface, Raman spectroscopy, and IR research. The electron transport characteristics of the OLi3@PDI-Imidazole surface was significantly enhanced in comparison to the PDI-Imidazole surface by lowering the bandgap energies from 1.27 eV to 1.03 eV. In contrast to the pure PDI-Imidazole surface, which had lower values for linear polarizability ( α0 ) (547.08 au) and first hyperpolarizability ( β0 )(201.133au), OLi3@PDI-Imidazole surface displayed significant enhancements in linear polarizability ( α0 = 706.472 au) and first hyperpolarizability ( β0 = 21314.360 au). It was observed by TD-DFT calculations that all the compounds had appreciable improvements in their interaction energies, HOMO–LUMO and UV–vis absorption and vertical ionization potential. Future development of nonlinear optical (NLO) devices has been discovered to benefit from the addition of OLi3 to the PDI-Imidazole surface.

Pattern recognition of multiple metal ions using fluorescent Perylenyl nanoaggregates and application in food traceability

Metal ions (MIs) identification is essential for the safety assessment, traceability and authentication of food. Most current approaches for detecting MIs are difficult to reconcile the simplicity, sensitivity and stability simultaneously. In this work, we proposed a novel strategy for discriminating MIs based on fluorescent supramolecular nanoaggregates (SNAs). In the presence of MI, perylene diimide derivatives (PDI)-based SNAs could be formed through the multiple non-covalent interactions between them including electrostatic, coordination and π-π interactions. With the assistance of discriminant analysis (LDA), different MIs (Hg2+, Ag+, Cd2+, Fe3+, Cr3+, Fe2+, Zn2+, Cu2+ and Pb2+) were successfully identified at three different concentration levels. It featured good quantitative sensing abilities in buffer solutions and practical samples. Furthermore, a water-quality evaluation model was successfully constructed for the distinction of different sources of drinking water, and the fluorescence array sensor technology was applied for the first time to the geographical traceability of apples.

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.

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.

Synthesis and characterization of new naphthalene diimides (NDIs) for application in electronic devices

This paper describes the synthesis of new naphthalene diimide (NDI) derivatives obtained in good yields from the reaction between 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA) and different p-alkoxy-substituted anilines. The photophysical properties of the NDIs were investigated in solution and the solid state. UV–visible absorption spectra in 1,4-dioxane, dichloromethane, and acetonitrile showed absorption maxima at approximately 375 nm, related to symmetry and spin allowed 1π-π* electronic transitions. These compounds did not exhibit fluorescence emission in the studied solvents. Electrochemical studies have indicated that the presence of different alkyl chains significantly affects the capacity of NDIs when used as organic cathodes in Al-graphite batteries due to variations in their ability to intercalate tetrachloroaluminate. The organic cathodes incorporating NDIs with varying alkyl chain lengths exhibited distinct capacities: 123.5 mA h g⁻1 for 3a, 101.6 mA h g⁻1 for 3b, and 157.3 mA h g⁻1 for 3c, with a capacity retention of approximately 54 % after 15 charge‒discharge cycles. These findings highlight the crucial role of alkyl chain modification in optimizing the electrochemical performance of organic cathodes.

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”

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.