Search Results (23)

Perylenediimide derivatives are materials that exhibit singlet fission (SF), capable of absorbing a single photon to generate multiple triplet excitons. This exciton multiplication process holds the potential to surpass the Shockley-Queisser limit. To effectively harness the energy of triplet excitons, they must possess sufficient diffusion capability. However, the diffusion of triplet excitons in perylenediimide derivatives has rarely been studied. In this work, we synthesized perylenediimide derivative crystals (C5) and fabricated composites (C5-Pe-QDs) by incorporating surface-ligand-functionalized quantum dots (Pe-QDs) at varying concentrations. The Pe-QDs act as traps within the C5 crystals, capturing triplet excitons when they diffuse into their capture range. The experimental and computational results indicate that the diffusion coefficient of triplet excitons in C5 crystals is approximately 3.58 × 10⁻⁵ cm² s⁻¹, with a diffusion length of about 50.9 nm. Using Monte Carlo simulations, we estimated the triplet exciton capture probability by Pe-QDs under ideal distribution conditions to be around 79.5%. The above findings indicate that, in the C5-Pe-QDs composites, triplet excitons can efficiently diffuse to the quantum dots, providing a novel and viable pathway for the effective utilization of triplet exciton energy in silicon-based photovoltaic systems. Full article

Perylenediimides are an interesting group of compounds that are finding more and more applications. However, the synthetic route of obtaining and modifying them is usually very complicated, costly, and time-consuming. Therefore, the conducted research aimed to develop new, greener, electrochemical methods of obtaining unknown perylenediimides (containing 2-ethylhexyl at the nitrogen atom). For the products obtained in this way, optical and electrochemical studies were conducted and compared with DFT results (i.e., energy gaps and HOMO and LUMO levels). Asa result of optical studies, different emission wavelengths of two isomers originating from the same excitation wavelength were observed. Electrochemical studies also confirmed significant differences in properties between the obtained isomers. Spectroelectrochemical measurements were also performed; they revealed the electrochromic properties of the obtained isomers in the visible and near-infrared range. Considering all the properties (optical and (spectro)electrochemical), the obtained compounds have a high potential for use in optoelectronic devices. Moreover, unprecedented pi-expansion of cis-DBPDI via 1,2-bis(p-bromophenyl)acetylene Diels–Alder cycloaddition into the bay region was also realized successfully. Summing up, electrosynthesis and further pi-expansion via cycloaddition offer a sea of opportunities for obtaining nanographenes. Full article

The screening of environmentally friendly, efficient and high-temperature-resistant organic corrosion inhibitors represents a significant means of reducing metal losses in industrial production. In this study, we investigated using aliphatic amine-functionalized perylene-diimide (PDINN) to inhibit Q235 steel in 1 M HCl media. The results show that PDINN significantly inhibits corrosion of Q235 steel in 1 M HCl. It is of greater significance that PDINN’s inhibition is unresponsive to temperature fluctuations in the corrosive environment, maintaining an efficiency of 86.5% at an ambient temperature of 328 K. DFT and MD analyses indicate that the exceptional inhibitory capacity of PDINN is closely associated with the extensive conjugated structure within the molecule, where it is firmly adsorbed on the Fe (110) via π-electrons. Full article

The rational design of ordered chromogenic supramolecular polymeric systems is critical for the advancement of next-generation stimuli-responsive, optical, and semiconducting materials. Previously, we reported the design of a stimuli-responsive, lamellar self-assembled platform composed of an imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and a commercially available diacid-functionalized diacetylene monomer, 10, 12 docosadiynedioic acid, in a 1:1 molar ratio. Herein, we expound on the importance of the composition of the imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and 10, 12 docosadiynedioic acid in the ratio of 2:1 to the supramolecular self-assembly, final morphology, and properties. Topochemical polymerization of the drop-cast films by UV radiation yielded blue-phase polydiacetylene formation, and subsequent thermal treatment of the films produced a thermoresponsive blue-to-red phase transformation. Differential scanning calorimetry (DSC) studies revealed a dual dependence of the methylene spacer length and stimuli treatment (UV and/or heat) on the thermal transitions of the films. Furthermore, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) showed well-defined hierarchical semiconducting nanostructures with interconnected “chessboard”-patterned lamellar stacking. Upon doping with an ionic liquid, the 2:1 platform showed higher ionic conductivity than the previous 1:1 one. The results presented here illustrate the importance of the composition and architecture to the ionic domain connectivity and ionic conductivity, which will have far-reaching implications for the rational design of semiconducting polymers for energy applications including fuel cells, batteries, ion-exchange membranes, and mixed ionic conductors. Full article

Perylenediimides (PDIs) are composed of a central perylene ring, on which are grafted two imide groups at the peri positions. Thionated PDIs are characterized by the substitution of one or more oxygen atoms of these imide functions with sulfur atoms. This structural modification alters the electronic properties with a redshift of the optical absorption accompanied by modification of the charge transport characteristics compared to their non-thionated counterparts. These properties make them suitable candidates for applications in optoelectronic devices, such as organic light-emitting diodes and organic photovoltaics. Moreover, the presence of sulfur atom(s) can favor the promotion of reactive oxygen species production for photodynamic and photothermal therapies. These thionated PDIs can be synthesized through the post-functionalization of PDIs by using a sulfurizing reagent. Nevertheless, the main drawbacks remain the difficulties in adjusting the degree of thionation and obtaining tri- and tetrathionated PDIs. Up to now, this thionation reaction has been described almost exclusively using Lawesson’s reagent. In the current study, we present our first investigations into an alternative reagent to enhance selectivity and achieve a greater degree of thionation. The association of phosphorus pentasulfide with hexamethyldisiloxane (Curphey’s reagent) clearly demonstrated higher reactivity compared with Lawesson’s reagent to attain multi-thionated PDIs. Full article

The spontaneous formation of self-sorted columnar structures of electron-donating and accepting π-conjugated molecules is attractive for photoconducting and photovoltaic properties. However, the simple mixing of donor–acceptor discotic molecules usually results in the formation of mixed-stacked or alternating-stacked columns. As a new strategy for overcoming this problem, here, we report the “side-chain labeling” approach using binary discotic systems and realize the preferential formation of such self-sorted columnar structures in a thermodynamically stable phase. The demonstrated key strategy involves the use of hydrophobic and hydrophilic side chains. The prepared blend is composed of liquid crystalline phthalocyanine with branched alkyl chains (H₂Pc) and perylenediimide (PDI) carrying alkyl chains at one side and triethyleneglycol (TEG) chains at the other side (PDI_C12/TEG). To avoid the thermodynamically unfavorable contact among hydrophobic and hydrophilic chains, PDI_C12/TEG self-assembles to stack up on top of each other and H₂Pc as well, forming a homo-stacked pair of columns (self-sort). Importantly, H₂Pc and PDI_C12/TEG in the blend are macroscopically miscible and uniform, and mesoscopically segregated. The columnar liquid crystalline microdomains of H₂Pc and PDI_C12/TEG are homeotropically aligned in a glass sandwiched cell. The “labeling” strategy demonstrated here is potentially applicable to any binary discotic system and enables the preferential formation of self-sorted columnar structures. Full article

Perylenediimide (PDI) compounds are widely used as the active units of thin-film organic lasers. Lately, PDIs bearing two sterically hindering diphenylphenoxy groups at the 1,7-bay positions have received attention because they provide a way to red-shift the emission with respect to bay-unsubstituted PDIs, while maintaining a good amplified spontaneous emission (ASE) performance at high doping rates. Here, we report the synthesis of a series of six PDI derivatives with different aryloxy groups (PDI 6 to PDI 10) or ethoxy groups (PDI 11) at the 1,7 positions of the PDI core, together with a complete characterization of their optical properties, including absorption, photoluminescence, and ASE. We aim to stablish structure-property relationships that help designing compounds with optimized ASE performance. Film experiments were accomplished at low PDI concentrations in the film, to resemble the isolated molecule behaviour, and at a range of increasing doping rates, to investigate concentration quenching effects. Compounds PDI 10 and PDI 7, bearing substituents in the 2′ positions of the benzene ring (the one contiguous to the linking oxygen atom) attached to the 1,7 positions of the PDI core, have shown a better threshold performance, which is attributed to conformational (steric) effects. Films containing PDI 11 show dual ASE. Full article

The synthesis and characterization of two new water soluble 2,6-bis(imidazolylmethyl)-4-methylphenoxy-containing perylenediimides, PDI-1 and PDI-2, are described. These compounds demonstrate a high fluorescence quantum yield in water and were investigated as potential photosensitizers for generating reactive oxygen species with applications in anticancer activities. The HeLa cell line (VPH18) was used to evaluate their efficacy. Fluorescence microscopy was employed to confirm the successful internalization of PDI-1 and PDI-2, while confocal microscopy revealed the specific locations of both PDIs within the lysosomes and mitochondria. In vitro studies were conducted to evaluate the anticancer activity of PDI-1 and PDI-2. Remarkably, these photosensitizers demonstrated a significant ability to selectively eliminate cancer cells when exposed to a specific light wavelength. The water solubility, high fluorescence quantum yield, and selective cytotoxicity of these PDIs toward cancer cells highlight their potential as effective agents for targeted photodynamic therapy. In conclusion, the findings presented here provide a strong foundation for the future exploration and optimization of PDI-1 and PDI-2 as effective photosensitizers in photodynamic therapy, potentially leading to improved treatment strategies for cancer patients. Full article

Electron transport materials (ETMs) play a vital role in electron extraction and transport at the perovskite/ETM interface of inverted perovskite solar cells (PSCs) and are useful in power conversion efficiency (PCE), which is limited by interface carrier recombination. However, strategies for passivating undercoordinated Pb²⁺ at the perovskite/ETM interface employing ETMs remain a challenge. In this work, a variety of heteroatoms were used to strengthen the Lewis base property of new ETMs (asymmetrical perylene-diimide), aimed at deactivating non-bonded Pb²⁺ at the perovskite surface through Lewis acid-base coordination. Quantum chemical analysis revealed that novel ETMs have matched the energy level of perovskite, which enables electron extraction at the perovskite/ETM interface. The results also suggest that the large electron mobility (0.57~5.94 cm² V⁻¹ s⁻¹) of designed ETMs shows excellent electron transporting ability. More importantly, reinforced interaction between new ETMs and Pb²⁺ was found, which is facilitating to passivation of the defects induced by unsaturated Pb²⁺ at the perovskite/ETM interface. Furthermore, it is found that MA (CH₃NH₃⁺), Pb, and I_Pb (iodine substituted on the Pb site) defects at the perovskite/ETM interface could be effectively deactivated by the new ETMs. This study provides a useful strategy to design ETMs for improving the interface property in PSCs. Full article

The emblematic perylenediimide (PDI) motif which was initially used as a simple dye has undergone incredible development in recent decades. The increasing power of synthetic organic chemistry has allowed it to decorate PDIs to achieve highly functional dyes. As these PDI derivatives combine thermal, chemical and photostability, with an additional high absorption coefficient and near-unity fluorescence quantum yield, they have been widely studied for applications in materials science, particularly in photovoltaics. Although PDIs have always been in the spotlight, their asymmetric counterparts, perylenemonoimide (PMI) analogues, are now experiencing a resurgence of interest with new efforts to create architectures with equally exciting properties. Namely, their exceptional fluorescence properties have recently been used to develop novel systems for applications in bioimaging, biosensing and photodynamic therapy. This review covers the state of the art in the synthesis, photophysical characterizations and recently reported applications demonstrating the versatility of these two sister PDI and PMI compounds. The objective is to show that after well-known applications in materials science, the emerging trends in the use of PDI- and PMI-based derivatives concern very specific biomedicinal applications including drug delivery, diagnostics and theranostics. Full article

Non-fullerene acceptors have recently attracted tremendous interest due to their potential as alternatives to fullerene derivatives in bulk-heterojunction solar cells. Nevertheless, physical understanding of charge carrier generation and transfer mechanism that occurred at the interface between the non-fullerene molecule and donor polymer is still behind their enhanced photovoltaic performance. Here we report examples of a non-planar perylene dimer (TP) as an electron acceptor and achieve a power conversion efficiency of 6.29% in a fullerene-free solar cell. Photoluminescence (PL) measurements show high quenching efficiency driven by the excitons of both conjugated polymer and TP molecule, respectively, indicating efficient electron and hole transfer, which can support a highly intermixed phase of blends measured by atomic force microscopy (AFM) and grazing incident wide-angle X-ray diffraction (GIWAXS). Femtosecond transient absorption spectroscopy (fs-TAS) reveals that the fast exciton dissociation process from TP molecule to donor polymer contributes to additionally increasing current density, leading to stronger incident photon to current efficiency in the visible region. Full article

A new family of perylenediimide (PDI) silver and copper complexes has been successfully synthesized by reacting ortho- and bay-substituted (dipyrid-2′,2″-ylamino)perylenediimide ligands with metal phosphine fragments. The coordination of the metal center did not reveal a significant effect on the photophysical properties, which are mainly due to the PDI ligands, and in some cases quenching of the luminescence was observed. The antiproliferative effect of the free perylenediimide ligands and the metalloPDI complexes against the cervix cancer cell line HeLa was determined by MTT assay. The free perylenediimide ligands exhibited a moderate cytotoxic activity, but the coordination of silver or copper to the dypyridylamino fragment greatly enhanced the activity, suggesting a synergistic effect between the two fragments. In attempts to elucidate the cellular biodistribution of the PDIs and the complexes, a colocalization experiment using specific dyes for the lysosomes or mitochondria as internal standards revealed a major internalization inside the cell for the metal complexes, as well as a partial mitochondrial localization. Full article

An overview of the different covalent bonding synthetic strategies of two electron acceptors leading to fullerene-perylenediimide (C₆₀-PDI)-based systems, essentially dyads and triads, is presented, as well as their more important applications. To go further in the development of such electron and photoactive assemblies, an original aromatic platform 5-benzyloxy-3-formylbenzoic acid was synthesized to graft both the PDI dye and the fullerene C₆₀. This new C₆₀-PDI dyad exhibits a free anchoring phenolic function that could be used to attach a third electro- and photoactive unit to study cascade electron and/or energy transfer processes or to obtain unprecedented side-chain polymers in which the C₆₀-PDI dyads are attached as pendant moieties onto the main polymer chain. This C₆₀-PDI dyad was fully characterized, and cyclic voltammetry showed the concomitant reduction process onto both C₆₀ and PDI moieties at identical potential. A quasi-quantitative quenching of fluorescence was demonstrated in this C₆₀-PDI dyad, and an intramolecular energy transfer was suggested between these two units. After deprotection of the benzyloxy group, the free hydroxyl functional group of the platform was used as an anchor to reach a new side-chain methyl methacrylate-based polymer in which the PDI-C₆₀ dyad units are located as pendants of the main polymer chain. Such polymer which associates two complementary acceptors could find interesting applications in optoelectronics and in particular in organic solar cells. Full article

Four new compounds from perylene dianhydride were prepared and tested for their anti-corrosion properties. Dizinc salt of perylene-3,4,9,10-tetracarboxylic acid and dimagnesium salts of perylene-3,4,9,10-tetracarboxylic acid, 5,5′-(1,3,8,10-tetraoxo-1,3,8,10-tetrahydroanthra[2,1,9-def:6,5,10-d′e′f′] diisoquinoline-2,9-diyl) bis(2-hydroxybenzoic acid) and N,N′-bis[3,3′-(dimethylamino)propylamine]-3,4,9,10-perylenediimide were characterized by analytical methods (SEM, EDX, X-ray) and parameters used in the field of paints (density, oil number and critical volume concentrations of pigment). The pigments (in a pigment volume concentration series) were used to prepare paints also containing a perylene C₂₆H₁₄N₂O₄ (Compound I) derivative pigment plus inert titanium dioxide to maintain a constant concentration of solids in the paint film. A mixture containing zinc nitroisophthalate and both the perylene derivative and titanium dioxide served as the reference material. The paints were applied to steel panels in two layers with a ruler. The organic coatings were subjected to electrochemical measurements and accelerated cyclic corrosion tests. The highest corrosion resistance was found for the coating containing C₂₄H₈O₈Mg₂. Superior to the coating containing either C₂₆H₁₄N₂O₄ or the conventional corrosion inhibitor C₈H₅N0₆-Zn, this pigment type acted mainly by a mechanism based on the compound’s complexation capacity at the metallic surface/organic coating/corrosion medium interface. The organic coatings containing perylene acid salts also attained high mechanical resistance. Full article

In the face of anthropogenic global warming the design and synthesis of materials, which enable energy transfer processes using sunlight as an energy source, are of high interest. Perylenediimides are a highly absorbing class of chromophores suitable for sunlight absorption and conversion. Therefore, metal–organic frameworks (MOFs) and coordination polymers (CPs) with incorporated organic perylene chromophores are highly interesting materials both for applied, but also fundamental, photophysical research. MOFs/CPs have the advantage of a modular adjustability of interchromophoric distances and angles, and the choice of metal nodes can be used to further tune the material towards the desired photophysical properties. In the present paper, we present a study using a reported organic perylenediimide (PDI) chromophore (H₂tpdb) as a linker to be incorporated into coordination polymer and test towards applicability within the photochemical ¹O₂ generation. In detail, a novel zinc 2D -coordination polymer Zn(tpdb)(DMF)₃ is reported, which is synthesized using a solvothermal synthesis with Zn(NO₃)₂ and a ditopic organic perylene linker. Both the linker and Zn-CP are fully characterized, including SC-XRD, showing a strong aggregation of tightly packed chromophores in the solid state. The photophysical properties are examined and discussed, including the observed shifts within the absorption spectra of the CP are compared to the linker in solution. These shifts are mainly attributed to the for PDIs known H-type aggregation and an additional charge transfer in the framework structure, causing a limited quantum yield of the emission. Finally, the photosensitization of triplet oxygen to singlet oxygen using 1,3-diphenylisobenzofurane (DBPF) as a trapping agent is investigated both for the free linker and the Zn-CP, showing that the perylene chromophore is an efficient photosensitizer and its activity can, in principle, be retained after its incorporation in the coordination polymer. Full article