Perylene Diimide Derivatives Research Articles

Synthesis and properties of bay unilaterally extended and mono-substituted perylene diimides

The synthesis of two sulfur-decorated perylene diimides, the five-membered S-heterocyclic annulated perylene diimide (1) and 1-propanethiol- N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (2), and a novel sulfoxide-containing perylene diimide, 1-propyl sulfoxide- N,N′-dicyclohexylperylene-3,4,9,10-tetracarboxylic diimide (3), are reported. The photophysical, electrochemical, aggregation, and thermal properties of these compounds are investigated by ultraviolet visible absorption, fluorescence, cyclic voltammetric, X-ray diffraction, and thermogravimetric analysis techniques. The geometries of the compounds are optimized at the 6-31G* level of theory using density functional theory, and their potentials are correlated with molecular orbitals. The prepared perylene diimide derivatives exhibit narrow the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals band gaps, and they have quite different absorptions and emissions in dichloromethane solutions, which are in agreement with the density functional theory–calculated results.

Facile Synthesis and Evaluation of Electron Transport and Photophysical Properties of Photoluminescent PDI Derivatives.

Perylenediimides (PDIs) have emerged as potential materials for optoelectronic applications. In the current work, four PDI derivatives, substituted at imide nitrogen with 2,6-diisopropyl phenyl, 2-nitrophenyl, diphenylmethylene, and pentafluorophenyl groups, have been synthesized from perylene 3,4,9,10-tetracarboxylic dianhydride using a facile imidization synthesis process. PDI derivatives have been spectroscopically characterized for their structure and optical properties. Temperature-variable absorption and emission spectroscopy study confirmed the H-aggregation property. H-aggregation along with strong emission suggests the slipped π–π stacking of PDI molecules. Electrochemical analysis was performed for their redox behavior and calculation of lowest unoccupied molecular orbital and highest occupied molecular orbital energy levels. Scanning electron microscopy showed the formation of ordered structures. The PDI derivatives showed excellent electron conductivity without doping and 5–10× higher electron mobility than that of state-of-the-art fullerene acceptor phenyl-C61-butyric acid methyl ester (PC61BM). Finally, the charge generation and charge transfer phenomenon was studied by transient absorption spectroscopy (TAS). TAS showed ultrafast charge transfer from the poly(3-hexyl)thiophene (P3HT) donor polymer to PDI and formation of long-lived charge-separated states similar to fullerene derivative PC61BM/P3HT blends. Such PDI derivatives with excellent solubility and photophysical and electronic properties are potential n-type materials to be used in organic electronic devices.

Redox-mediated Negative Differential Resistance (NDR) Behavior in Perylenediimide Derivative: A Supramolecular Approach.

Deaggregated perylenediimide (PDI) derivatives exhibit exceptionally high quantum yields, photostability and appropriate molecular features for organic electronics. This work demonstrates a metal-dye-metal framework with a large and stable negative differential resistance (NDR) at ambient conditions, built using a supramolecular strategy. The deaggregation achieved through the encapsulation of the bay-substituted phenyl groups of aggregated (l/d)-Phe-PDI dyes by the β-CD macrocyclic host is validated through detailed spectroscopic and imaging techniques. The host-guest interaction resulted in a dramatic enhancement in the emission yield from 0.28 to 0.90. In the thin film deposits, the β-CD/(l/d)-Phe-PDI complex displayed well-connected sheet-like morphology, whereas the uncomplexed (l/d)-Phe-PDI dye remained as scattered lumps. The large and reversible I-V characteristics displaying strong NDR behavior is attributed to the oxidation/reduction processes involving the rigid π-rich PDI core and is stable at least for about six months at ambient conditions, a promising system for organic electronics applications.

Interplay between Charge Carrier Mobility, Exciton Diffusion, Crystal Packing, and Charge Separation in Perylene Diimide-Based Heterojunctions.

Two of the key parameters that characterize the usefulness of organic semiconductors for organic or hybrid organic/inorganic solar cells are the mobility of charges and the diffusion length of excitons. Both parameters are strongly related to the supramolecular organization in the material. In this work we have investigated the relation between the solid-state molecular packing and the exciton diffusion length, charge carrier mobility, and charge carrier separation yield using two perylene diimide (PDI) derivatives which differ in their substitution. We have used the time-resolved microwave photoconductivity technique and measured charge carrier mobilities of 0.32 and 0.02 cm2/(Vs) and determined exciton diffusion lengths of 60 and 18 nm for octyl- and bulky hexylheptyl-imide substituted PDIs, respectively. This diffusion length is independent of substrate type and aggregate domain size. The differences in charge carrier mobility and exciton diffusion length clearly reflect the effect of solid-state packing of PDIs on their optoelectronic properties and show that significant improvements can be obtained by effectively controlling the solid-state packing.

Electronic energy levels in lyotropic chromonic liquid crystals formed by ionic perylene diimide derivatives

Lyotropic Chromonic Liquid Crystals (LCLCs) represent dispersions of disk-like organic molecules in water that form columnar aggregates bound together by weak hydrophobic interactions and aligned parallel to each other. Dry films of LCLCs preserve the aggregated molecular packing and orientational order. Our idea is that this class of materials is ideally suited for flexible electronics applications since their structure is shaped by relatively weak non-covalent molecular interactions. We report an experimental study that aims to elucidate the influence of ionic substitutes on the energy band of LCLCs based on perylene-diimide derivatives. Using cyclic voltammetry and light absorption techniques, we explore the role of functionalization of several materials of this class with ionic end groups (positive and negative) on the molecular LUMO/HOMO energy level positions. We find that both positively and negatively charged LCLC molecules show decrease in energy positions in comparison with chemically-similar non-mesogenic materials. The experimentally estimated parameters show the deep-lying LUMO energy levels (below −4.0 eV) for all studied LCLC materials with ionic substitutes.

Perylene derivatives for solar cells and energy harvesting: a review of materials, challenges and advances

Herein, we present a review about recent advances in perylene diimide derivatives applied to organic solar cells and energy harvesting. Several organic and inorganic compounds, most of which are solution processed or thermally evaporated, are used for this purpose. Features such as energy level in relation to the donor material’s thermal and mechanical stability and processability are among the aspects that reflect the performance of these materials as electron acceptors or electrodes. Moreover, the donor/acceptor interface directly reflects the photovoltaic response. Therefore, device engineering efforts have been exerted to achieve proper acceptor distribution along the bulk of thin films or improve the compatibility at the donor/acceptor interface. This review is divided into subsections concerning the use of PDI molecules, PDI dimers/trimers/tetramers, bilayer devices, routes to improve the donor/acceptor interface, PDI-based polymers and energy harvesting. The reports show that PDI derivatives are suitable candidates for replacing fullerene derivatives in OSCs with reduced production cost and improved stability. Moreover, new PDI composites with graphene are promising cathodes for sodium batteries. Therefore, PDI derivatives are low cost and multifunctional materials employed to produce optoelectronic devices with numerous purposes.

Electrochemical Study of Structure Tunable Perylene Diimides and The Nanofibers Deposited on Electrodes.

The electrochemical behavior of organic conjugated semiconductors and their bulk materials is a considerable and irreplaceable parameter to maintain their diverse electronic or optoelectronic applications. In this paper, a series of n-type symmetrical perylene diimide derivatives (PTCDIs) with substituents (3,4-ethylenedioxythiophene (EDOT), cyclohexane, acetic acid, or propionic acid) at located the nitrogens imide position were synthesized, and their solubility, optical features, thermal stability, as well as solution-phase interfacial self-assembly into one-dimensional (1D) nanofibers and related morphology were discussed in detail. Moreover, a simple but effective method, in situ deposition following in situ self-assembly, was developed to construct uniform electrodes over a large area coated with networked PTCDI nanofibers. Then the electrochemical properties of the PTCDI nanofibers were researched in comparison with their molecules. The excellent variability at molecular or nanoscale morphological level will provide an interesting insight into the research of PTCDIs in a wide range applications of organic electronics.

Modular Molecular Nanoplastics.

In view of their facile fabrication and recycling, functional materials that are built from small molecules ("molecular plastics") may represent a cost-efficient and sustainable alternative to conventional covalent materials. We show how molecular plastics can be made robust and how their (nano)structure can be tuned via modular construction. For this purpose, we employed binary composites of organic nanocrystals based on a perylene diimide derivative, with graphene oxide (GO), bentonite nanoclay (NC), or hydroxyethyl cellulose (HEC), that both reinforce and enable tailoring the properties of the membranes. The hybrids are prepared via a simple aqueous deposition method, exhibit enhanced mechanical robustness, and can be recycled. We utilized these properties to create separation membranes with tunable porosity that are easy to fabricate and recycle. Hybrids 1/HEC and 1/NC are capable of ultrafiltration, and 1/NC removes heavy metals from water with high efficiency. Hybrid 1/GO shows mechanical properties akin to covalent materials with just 2-10% (by weight) of GO. This hybrid was used as a membrane for immobilizing β-galactosidase that demonstrated long and stable biocatalytic activity. Our findings demonstrate the utility of modular molecular nanoplastics as robust and sustainable materials that enable efficient tuning of structure and function and are based on self-assembly of readily available inexpensive components.

Bacteria‐Assisted Selective Photothermal Therapy for Precise Tumor Inhibition

AbstractPhotothermal therapy (PTT) has drawn extensive research attention as a promising approach for tumor treatment. In this study, a bacteria‐assisted strategy relying on the selective reduction of perylene diimide derivative based supramolecular complex (CPPDI) to radical anions (RAs) by Escherichia coli in hypoxic tumors is developed to realize highly precise PTT of tumors. Noninvasive E. coli are first injected intravenously for selectively accumulating and replicating in the tumor due to the hypoxia tropism. Then, CPPDI is loaded in a peptide‐hybrid matrix metalloproteinase‐2 (MMP‐2) responsive liposome (MRL) and injected intravenously. After accumulated and released from MRL in the tumor where MMP‐2 is overexpressed, CPPDI is reduced by E. coli in the hypoxic tumor environment to produce CPPDI RAs (CRAs), which serve as effective photothermal agents for tumor cells thermal ablation under near‐infrared light irradiation. Since E. coli accumulate and grow in tumor sites selectively, this strategy accurately limits the production of CRAs in tumors for highly selective PTT, which will find great potential for precise tumor inhibition.

Design of an Amphiphilic Perylene Diimide for Optical Recognition of Anticancer Drug through a Chirality-Induced Helical Structure.

Introduction of chirality into a supramolecular self-assembly system plays an indispensable role in attaining specific molecular recognition ability. Herein, a chiral anticancer drug 5'-deoxy-5-fluorouridine (5'DFU) was explored for inducing the self-assembly of a cationic perylene diimide derivative containing boronic acid groups (PDI-PBA) into a highly ordered right-handed helical structure. As a result, PDI-PBA exhibited a molecular recognition ability towards 5'DFU among other cis-diols and anticancer drugs. With the help of a dynamic covalent bond and favorable hydrogen-bonding interactions, chirality transfer from chiral 5'DFU to achiral PDI-PBA breaks down the strong π-π stacking of PDI-PBA and makes it reorganize into highly ordered helical supramolecular structures. This work provides an insight into chiral anticancer drug tuning interactions of π-chromophores and the inducement of hierarchical self-assembly to achieve specific molecular recognition.

Organosiloxane and Polyhedral Oligomeric Silsesquioxanes Compounds as Chemiluminescent Molecular Probes for Direct Monitoring Hydroxyl Radicals.

Despite the tremendous progress in the research of luminescent probes for reactive oxygen species (ROS), designing luminescent ROS probes with high sensitivity for the individual ROS is still retarded because of their high reactivity and the rapid and complex interconversion reactions among them. Herein, organosiloxane and polyhedral oligomeric silsesquioxanes (POSS) compounds are designed as a novel class of luminescent molecular probes to produce extraordinary chemiluminescence (CL) based on the specific electrophilic attack of •OH. No CL signal can be obtained by the other ROS and strong oxidants. AEAP-POSS formed by hydrolytical condensation of 3-(2-aminoethylamino)propyl]trimethoxysilane (AEAPTMS) is constructed to covalently link a dye molecular, perylene diimide derivative (PDI), and an intramolecular chemiluminescence resonance energy transfer (CRET) system is obtained to realize the red shift of CL wavelength and enhanced CL intensity. This probe based on CRET is applied to monitor inherent •OH in ambient particular matter (PM2.5 and PM10). Density functional theory (DFT), ion chromatograph, X-ray photoelectron spectroscopy (XPS), particle size analysis, and fluorescence spectrum (FL) are applied to study the CL mechanism. These studies discover that electronically carbonyl CH3CO• is the CL emitter, and the silicon-oxygen skeleton in the organosiloxane and POSS compounds plays the key role in undergoing chemiluminescence (CL) reaction.

Perylene diimide derivative regulate the antimony sulfide morphology and electrochemical sensing for hydrazine

Sb2S3/perylene diimide derivatives composite micro-spheres composed of slight dendrites were synthesized by solvothermal reaction. Perylene diimide derivative with two carboxyl groups at amine position as morphology-controlling reagent is the key factor for determining the microscopic morphology of Sb2S3 in this system. Time-dependent experiments have been conducted to track the formation of Sb2S3 micro-spheres. Moreover, the composite material showed an excellent sensitivity of 29.8 μA mM−1 cm2 with a low detection limit of 50 pM, it also showed better stability and selectivity in hydrazine detection. This approach not only regulate the morphology and composition of Sb2S3 submicron materials effectively, but also provide new ideas for the manufacture of metal sulfide- perylenediimide amino acid derivative materials, which will be suitable for sensing, catalysis, and photovoltaic applications.

A Silicon-Based Heterojunction Integrated with a Molecular Excited State in a Water-Splitting Tandem Cell.

Semiconductor-based photocathodes with high light-absorption capability are of interest in the production of solar fuels, but many of them are limited by low efficiencies due to rapid interfacial back electron transfer. We demonstrate here that a nanowire-structured p-type Si (p-Si) electrode, surface-modified with a perylene-diimide derivative (PDI'), can undergo photoreduction of a surface-bound, water reduction catalyst toward efficient H2 evolution under a low applied bias. At the electrode interface, the PDI' layer converts green light into high-energy holes at its excited state for extraction of photogenerated electrons at the photoexcited p-Si. The photogenerated electrons at the reduced PDI' are subsequently transferred to the molecular H2-evolution catalyst. Involvement of the photoexcited PDI' enables effective redox separation between the electrons at the reduced catalyst and the holes at the valence band of p-Si. The heterojunction photocathode was used in a tandem cell by coupling with a dye-sensitized photoanode for solar-driven water splitting into H2 and O2.

Star-shaped molecule with planar triazine core and perylene diimide branches as an n-type additive for bulk-heterojunction perovskite solar cells

A novel star-shaped molecule, TPDI, featuring a triazine unit as the core and units of a perylene diimide derivative as its conjugated branches, has been synthesized for application as an n-type additive in methylammonium lead iodide (CH3NH3PbI3, MAPbI3)–based bulk-heterojunction perovskite solar cells (PVSCs). The architecture of the PVSCs was indium tin oxide/poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate)/MAPbI3:TPDI/[6,6]-phenyl-C61-butyric acid methyl ester/Ag. The star-shaped molecule TPDI was added into the MAPbI3 layer to minimize grain boundary defects and enhance the coverage and crystal grain sizes of the perovskite film. Upon the incorporation of a suitable amount of TPDI, the defects of the perovskite crystals were compensated for, and the absorbance and electron-transfer ability of the photoactive active layer were enhanced, thereby improving the photovoltaic performance of the PVSC. An open-circuit voltage of 0.83 V, a short-circuit current of 19.2 mA cm−2, a fill factor of 0.68, and a photoconversion efficiency of 10.84% were obtained for the TPDI-doped PVSC.

Designing a Perylene Diimide/Fullerene Hybrid as Effective Electron Transporting Material in Inverted Perovskite Solar Cells with Enhanced Efficiency and Stability

Electron transport materials (ETM) play an important role in the improvement of efficiency and stability for inverted perovskite solar cells (PSCs). This work reports an efficient ETM, named PDI-C60 , by the combination of perylene diimide (PDI) and fullerene. Compared to the traditional PCBM, this strategy endows PDI-C60 with slightly shallower energy level and higher electron mobility. As a result, the device based on PDI-C60 as electron transport layer (ETL) achieves high power conversion efficiency (PCE) of 18.6 %, which is significantly higher than those of the control devices of PCBM (16.6 %) and PDI (13.8 %). The high PCE of the PDI-C60 -based device can be attributed to the more matching energy level with the perovskite, more efficient charge extraction, transport, and reduced recombination rate. To the best of our knowledge, the PCE of 18.6 % is the highest value in the PSCs using PDI derivatives as ETLs. Moreover, the device with PDI-C60 as ETL exhibits better device stability due to the stronger hydrophobic properties of PDI-C60 . The strategy using the PDI/fullerene hybrid provides insights for future molecular design of the efficient ETM for the inverted PSCs.

Designing a Perylene Diimide/Fullerene Hybrid as Effective Electron Transporting Material in Inverted Perovskite Solar Cells with Enhanced Efficiency and Stability

AbstractElectron transport materials (ETM) play an important role in the improvement of efficiency and stability for inverted perovskite solar cells (PSCs). This work reports an efficient ETM, named PDI‐C60, by the combination of perylene diimide (PDI) and fullerene. Compared to the traditional PCBM, this strategy endows PDI‐C60 with slightly shallower energy level and higher electron mobility. As a result, the device based on PDI‐C60 as electron transport layer (ETL) achieves high power conversion efficiency (PCE) of 18.6 %, which is significantly higher than those of the control devices of PCBM (16.6 %) and PDI (13.8 %). The high PCE of the PDI‐C60‐based device can be attributed to the more matching energy level with the perovskite, more efficient charge extraction, transport, and reduced recombination rate. To the best of our knowledge, the PCE of 18.6 % is the highest value in the PSCs using PDI derivatives as ETLs. Moreover, the device with PDI‐C60 as ETL exhibits better device stability due to the stronger hydrophobic properties of PDI‐C60. The strategy using the PDI/fullerene hybrid provides insights for future molecular design of the efficient ETM for the inverted PSCs.

Spectroscopic, electrochemical and electrocolorimetric properties of novel 2-(2′-pyridyl)-1H-benzimidazole appended bay-substituted perylene diimide triads

In this study, four new perylene diimide (PDI) derivatives incorporating 2-(2′-pyridyl)-1H-benzimidazole (2PBI) chromophores at the imide positions, in which 1 bearing non-bay-substituted perylene core, and those having four substituents at 1,6,7,12-bay positions of the perylene core, namely 2 bearing electron-withdrawing chlorine atoms, 3 bearing electron-donating 4-methoxyphenoxy groups and 4 bearing non-electron-donating 4-tert-butylphenoxy groups, respectively were synthesized and fully characterized by FT-IR, 1H NMR, 13C NMR, MALDI-TOF mass spectrometry and UV/Vis spectroscopy. The thermal properties were measured by thermogravimetric analysis (TGA) which showed that the materials (1-4) are thermally very stable (Td > 450 °C). DFT was performed for geometry optimizations, and TDDFT was used to compare the calculated and the experimental UV/Vis electronic spectra at the B3LYP/6–311 G(d) level. Detailed measurements were carried out by the use of electroanalytical, spectroscopic and colorimetric techniques in order to understand redox natures, color changes and optoelectronic characters of the novel compounds. These 2PBI-functionalized PDI triads showed reversible reduction processes, chemically stable reduced species and considerably low HOMO-LUMO band gaps, as the new worthy members of photoactive charge transport materials for optoelectronic and photovoltaic systems. In addition, with distinct color changes associated with their redox processes in the solution, these new triads displayed great capacity for application in electrochromic devices. The emission maxima of the compounds were found to be red shifted in the solid state.

Enhancement of Photocurrent by Integration of an Artificial Light-Harvesting Antenna with a Photosystem I Photovoltaic Device

Photosynthetic pigment–protein-based biophotovoltaic devices are attracting interest as environmentally friendly energy sources. Photosystem I (PSI), a photosynthetic pigment–protein, is a proven biophotovoltaic material because of its abundance and high charge separation quantum efficiency. However, the photocurrent of these biophotovoltaic devices is not high because of their low spectral response. We have integrated an artificial light-harvesting antenna into a PSI-based biophotovoltaic device to expand the spectral response. To fabricate the device, a perylene di-imide derivative (PTCDI) was introduced onto a TiO2 surface as an artificial antenna. In the photovoltaic cells formed by the PTCDI/PSI-assembled TiO2 electrode, the magnitude of the incident photon-to-current conversion efficiency spectrum was significantly enhanced in the range 450–750 nm, and the photocurrent increased to 0.47 mA/cm2. The result indicates that the photons absorbed by PTCDI transfer to PSI via Forster resonance energy transfer.

Multifunctional Gene Carriers Labeled by Perylene Diimide Derivative as Fluorescent Probe for Tracking Gene Delivery.

Multifunctional carriers with both gene transfection property and fluorescent tracking function have attracted significant attention in recent years. Herein, a kind of perylene diimide derivative (PDI-C10C8) is conjugated onto the polyethylenimine-g-poly(lactide-co-glycolide)-g-polyethylenimine (PLGA-PEI) polymer to obtain fluorescent multifunctional polymer and micelles (abbreviated as MP). Then, the REDV-G-TAT-G-NLS (TP-G) peptide sequence is grafted onto this MP to obtain multifunctional micelles labeled by perylene diimide derivative (MP-TP-G). These micelles exhibit enhanced photobleaching stability compared with the reference Cy5-labeled micelles, and the fluorescent images of cellular uptake show bright red emission without any background noise. Confocal laser scanning microscope (CLSM) experiments show that gene complexes can deliver gene into nucleus. MP-TP-G carriers do not enter into the cell nucleus, which proves that the nuclear localization signal sequence may not exert its nucleus accumulation ability via conjugating to the amphiphilic polymers. The high transfection efficiency and the enhanced photobleaching stability, combined with the ability to monitor the detailed process of cellular uptake and gene delivery, make these multifunctional micelles have great potential application for endothelialization of artificial blood vessels and gene delivery process study.

Covalently Linked Perylene Diimide-Polydiacetylene Nanofibers Display Enhanced Stability and Photocurrent with Reversible FRET Phenomenon.

Because of their unique structural and optical properties, 1D perylene diimide (PDI) derivatives have gained attention for use in optoelectronic devices. However, PDI-containing self-assembled supramolecular systems often are of limited use because they have supramolecular architectures that are held together by weak noncovalent π-π stacking, hydrogen bonding, and hydrophobic interactions. As a result, they are intrinsically unstable under solution-processing conditions. To overcome this limitation, a polydiacetylene (PDA)-based strategy is developed to construct a solvent-resistant and stable PDI assembly. For this purpose, first the monomer PDI-BisDA is generated, in which two polymerizable diacetylene (DA) units are covalently linked to a PDI core. Importantly, 254 nm UV irradiation of self-assembled PDI-BisDA nanofibers forms solvent-resistant and stable PDI-PDA fibers. Owing to the presence of PDA, the generated polymer fibers display an increased photocurrent. In addition, the existence of PDA and PDI moieties in the fiber leads to the occurrence of switchable on-off fluorescence resonance energy transfer (FRET) between the PDI and reversibly thermochromic PDA chromophores.