Perylene Derivatives Research Articles

Novel Ternary System for Electrochemiluminescence Biosensor and Application toward Pb2+ Assay.

This study constructed an electrochemiluminescence (ECL) biosensor for ultrasensitive detection of Pb2+ in a ternary system by employing DNAzyme. The ternary system is composed of a potassium-neutralized perylene derivative (K4PTC) as the ECL emitter, K2S2O8 as the coreactant, and neodymium metal-organic frameworks (Nd-MOFs) as the coreaction accelerators. Nd-MOFs immobilize DNAzymes and enhance the luminescence intensity of the K4PTC/K2S2O8 system. As part of this system, K4PTC enhances the ECL signal in solution and supports Pb2+ detection. The sequence of ferrocene (Fc)-linked DNA (DNA-Fc) is catalytically cleaved by DNAzymes in the presence of Pb2+. This causes the removal of DNA1-Fc from the electrode surface to recover the ECL signal. As a result, the as-prepared ECL biosensor can quantify Pb2+ with a detection limit (LOD) of 4.1 fM in the range of 1 μM to 10 fM. The ECL biosensor displays high specificity, good stability, excellent reproducibility, and desirable practicality for Pb2+ detection in tap water. Moreover, by simply changing the sequence of the DNAzyme, new biosensors can be designed for ultrasensitive detection of different heavy metal ions, offering an excellent approach for monitoring water quality safety.

Refinement of non-covalent interactions via hetero-seeded self-assembly for the pathway complexity control of perylene derivatives

The introduction of methodologies to amalgamate, shear, or fabricate structures could potentially lead to exceptionally remarkable architectures. In this work, three similar perylene-based molecules, PDI 1–3, each modified with different alkyl chains, were synthesized to investigate the pathway complexity via hetero-seeded self-assembly. Delightfully, a type of remarkably active metastable nanowires assemblied from perylene-based molecule PDI 1 was obtained. Based on this, hierarchical heterojunction microsheets were fabricated using metastable nanowires derived from PDI 1, initiated by hetero-seeds sourced from the perylene-based molecule PDI 2 in a "bottom-up" approach. Furthermore, the decomposition of the microsheet seed derived from PDI 3 was achieved, resulting in the formation of heterogeneous nanowires induced by the metastable nanowires from PDI 1 in a "top-down" approach. The decomposition and fabrication of the microsheet architectures were unveiled to be governed by the competitive π-interactions between seeds and monomers during the self-assembly process. This research is a powerful novel approach for assembling complex architectures and has enhanced the understanding of the molecular assembly growth process at the interface.

A systematic evaluation of Random Lasing, Third Harmonic Generation, and quantum chemical calculations in multifunctional perylene derivatives

The quest for multifunctional materials in the field of optoelectronics has become increasingly imperative, as it offers a pathway toward the development of highly versatile and efficient devices. In this study, we present a comprehensive overview of our achievements in the characterization of perylene derivative-based materials. This group of chromophores exhibits remarkable multifunctionality including Third Harmonic Generation (THG), Z-scan results, and excellent Random Lasing (RL) capabilities. Theoretical quantum chemical calculations (QCC) were conducted to investigate dipole moments, frontier molecular orbital HOMO and LUMO energies, optical band gap energies, as well as second hyperpolarizabilities (γ). The study revealed how groups attached to the perylene core influence the chromophore's dipole moment and, consequently, the nonlinear optical (NLO) properties of the investigated compounds. The combined theoretical and experimental analyses provide valuable insights for the design of various optoelectronic devices using thin films of perylene derivatives, enhancing the understanding of their nonlinear and laser action behavior.

A General Strategy for Food Traceability and Authentication Based on Assembly-Tunable Fluorescence Sensor Arrays.

Food traceability and authentication systems play an important role in ensuring food quality and safety. Current techniques mainly rely on direct measurement by instrumental analysis, which is usually designed for one or a group of specific foods, not available for various food categories. To develop a general strategy for food identification and discrimination, a novel method based on fluorescence sensor arrays is proposed, composed of supramolecular assemblies regulated by non-covalent interactions as an information conversion system. The stimuli-responsiveness and tunability of supramolecular assemblies provided an excellent platform for interacting with various molecules in different foods. In this work, five sensor arrays constructed by supramolecular assemblies composed of pyrene derivatives and perylene derivatives are designed and prepared. Assembly behavior and sensing mechanisms are investigated systematically by spectroscopy techniques. The traceability and authentication effects on several kinds of food from different origins or grades are evaluated and verified by linear discriminant analysis (LDA). It is confirmed that the cross-reactive signals from different sensor units encompassing all molecular interactions can generate a unique fingerprint pattern for each food and can be used for traceability and authentication toward universal food categories with 100% accuracy.

Stable n-Type Perylene Derivative Ladder Polymer with Antiambipolarity for Electrically Reconfigurable Organic Logic Gates.

Organic electrochemical transistors (OECTs) are one of the promising building blocks to realize next-generation bioelectronics. To date, however, the performance and signal processing capabilities of these devices remain limited by their stability and speed. Herein, the authors demonstrate stable and fast n-type organic electrochemical transistors based on a side-chain-free ladder polymer, poly(benzimidazoanthradiisoquinolinedione). The device demonstrated fast normalized transient speed of 0.56 ± 0.17 msum-2 and excellent long-term stability in aqueous electrolytes, with no significant drop in its doping current after 50 000 successive doping/dedoping cycles and 2-month storage at ambient conditions. These unique characteristics make this polymer especially suitable for bioelectronics, such as being used as a pull-down channel in a complementary inverter for long-term stable detection of electrophysiological signals. Moreover, the developed device shows a reversible anti-ambipolar behavior, enabling reconfigurable electronics to be realized using a single material. These results go beyond the conventional OECT and demonstrate the potential of OECTs to exhibit dynamically configurable functionalities for next-generation reconfigurable electronics.

Investigation of the photothermal properties of a large series of metal-bis(dithiolene) complexes: Impact of the molecular structure and ranking using the photothermal index IPT

The photothermal properties in the NIR region of a large series of 19 metal-bis(dithiolene) complexes and of a perylene derivative have been studied in detail. Photophysical and thermal measurements were repeated several times to obtain good uncertainties on molar extinction coefficients, temperature increases and photothermal efficiencies. This large series of metal-bis(dithiolene) complexes enabled us to assess the impact of the nature of the metal center, the nature of the ligand and the number and length of the carbon chains on absorption properties and photothermal efficiencies. Thanks to these reliable data, the recently introduced photothermal index IPT, which combines molar absorptivity ε and photothermal efficiency η, has also been effectively used to rank all these molecular photothermal agents according to their photothermal activity. This work confirms that the photothermal index IPT can be used effectively to rank photothermal agents according to their ability to convert light into heat.

Orientation Dependent Interlayer Coupling in Organic–Inorganic Heterostructures

AbstractOrganic–inorganic 2D heterostructures combine the high optical absorption of organic molecules with exciton‐dominated optical properties in layered transition metal dichalcogenides (TMDs) such as MoS2. Critical to the interaction and the optical response in such hybrid systems is the electronic band alignment at the interface between the two species. Here, the coupling of monolayers of perylene derivatives is investigated with bilayer MoS2. In particular, variation in the perylene orientation on the MoS2 surface is identified using Raman spectroscopy and scanning probe microscopy. Low‐temperature optical spectroscopy reveals orientation‐dependent interlayer exciton formation. Furthermore, power‐dependent photoluminescence measurements provide insight into the modified interlayer charge transfer in these heterostructures. A saturation of interlayer states is found under high excitation power when the perylene molecules are in a perpendicular orientation to the surface that leads to electron accumulation in the MoS2, whereas parallel alignment of the perylene molecules leads to enhanced populations of organic–inorganic interlayer excitons. This work provides insights into the optimization of organic–inorganic heterostructures, with particular relevance to applications for optoelectronic and excitonic devices.

Theoretical design of phosphorus-doped perylene derivatives as efficient singlet fission chromophores.

Singlet fission (SF) is considered as a promising strategy to overcome the Shockley-Queisser limit of single-junction solar cells. However, only a handful of chromophores were observed to undergo SF to date. To broaden the number of SF chromophores, we designed a series of phosphorus-doped perylenes based on the diradical character strategy and examined their SF feasibility using theoretical calculations. By analysis of frontier orbitals, diradical character and aromaticity, SF-capable candidates were prescreened. These analyses reveal that the diradical character of perylene is effectively enhanced by P-doping at bay- and peri-positions of perylene, making SF more thermodynamically feasible. However, the diradical character remains nearly unchanged when P atoms are doped at ortho-positions because the spin center cannot be stabilized, leading to a more endothermic SF. This study shows how SF-related energies and diradical character of SF chromophores are altered by P doping, and extends the SF-capable molecular library.

Recent Progress and Challenges in Perylene Small Molecules, Assemblies and Composites for Photocatalytic Hydrogen Evolution

AbstractPerylene diimide (PDI) derivatives are among the best‐known n‐type organic semiconductors because of their unique photophysical and chemical characteristics. In recent years, significant progress has been made in the development of various PDI/composites and their self‐assembled structures for photocatalytic hydrogen (H2) evolution. However, the slow transport of photogenerated charge carriers, rapid charge recombination, limited catalytic activity, and instability of these materials still pose difficulties for their practical use. In order to address these problems, extensive studies have been conducted on structural modifications, molecular design, and synthesis techniques to control the morphology of self‐assembled PDI structures and create new and effective photocatalysts. In this context, perylene based small molecules, their composites with TiO2 and g‐C3N4, self‐assembled perylene derivatives have been designed and their roles as heterogenous photocatalysts for H2 evolution have been investigated thoroughly in literature. In this review, the developments of PDI‐based photocatalysts for H2 evolution are outlined under four different categories. Self‐assembled PDI nanostructures have made the most advancements among all the categories, with highest hydrogen evolution rate (HER) of 61.49 mmol g−1 h−1 while composites composed of perylene derivatives and g‐C3N4 exhibited the second highest rate of hydrogen evolution (17.7 mmol g−1 h−1). This review is intended to give researchers a better understanding and guidelines for designing PDI‐based and other chromophore‐based materials for efficient H2 evolution and their further exploration for future improvement in H2 evolution efficiencies.

Lateral epitaxial growth of two-dimensional organic heterostructures.

Two-dimensional organic lateral heterostructures (2D OLHs) are attractive for the fabrication of functional materials. However, it is difficult to control the nucleation, growth and orientation of two distinct components. Here we report the combination of two methods-liquid-phase growth and vapour-phase growth-to synthesize 2D OLHs from perylene and a perylenecarboxaldehyde derivative, with a lateral size of ~20 μm and a tunable thickness ranging from 20 to 400 nm. The screw dislocation growth behaviour of the 2D crystals shows the spiral arrangement of atoms within the crystal lattice, which avoids volume expansion and contraction of OLH, thereby minimizing lateral connection defects. Selective control of the nucleation and sequential growth of 2D crystals leads to structural inversion of the 2D OLHs by the vapour-phase growth method. The resulting OLHs show good light-transport capabilities and tunable spatial exciton conversion, useful for photonic applications. This synthetic strategy can be extended to other families of organic polycyclic aromatic hydrocarbons, as demonstrated with other pyrene and perylene derivatives.

Alkyl Derivatives of Perylene Photosensitizing Antivirals: Towards Understanding the Influence of Lipophilicity.

Amphipathic perylene derivatives are broad-spectrum antivirals against enveloped viruses that act as fusion inhibitors in a light-dependent manner. The compounds target the lipid bilayer of the viral envelope using the lipophilic perylene moiety and photogenerating singlet oxygen, thereby causing damage to unsaturated lipids. Previous studies show that variation of the polar part of the molecule is important for antiviral activity. Here, we report modification of the lipophilic part of the molecule, perylene, by the introduction of 4-, 8-, and 12-carbon alkyls into position 9(10) of the perylene residue. Using Friedel-Crafts acylation and Wolff-Kishner reduction, three 3-acetyl-9(10)-alkylperylenes were synthesized from perylene and used to prepare 9 nucleoside and 12 non-nucleoside amphipathic derivatives. These compounds were characterized as fluorophores and singlet oxygen generators, as well as tested as antivirals against herpes virus-1 (HSV-1) and vesicular stomatitis virus (VSV), both known for causing superficial skin/mucosa lesions and thus serving as suitable candidates for photodynamic therapy. The results suggest that derivatives with a short alkyl chain (butyl) have strong antiviral activity, whereas the introduction of longer alkyl substituents (n = 8 and 12) to the perylenyethynyl scaffold results in a dramatic reduction of antiviral activity. This phenomenon is likely attributable to the increased lipophilicity of the compounds and their ability to form insoluble aggregates. Moreover, molecular dynamic studies revealed that alkylated perylene derivatives are predominately located closer to the middle of the bilayer compared to non-alkylated derivatives. The predicted probability of superficial positioning correlated with antiviral activity, suggesting that singlet oxygen generation is achieved in the subsurface layer of the membrane, where the perylene group is more accessible to dissolved oxygen.

Photophysical Properties of Homo- and Hetero-Aggregate Assemblies Made of N-Annulated Perylene Derivatives.

We report the absorption spectra and photophysical properties of homo and hetero-aggregate assemblies of a strongly emissive N-annulated perylene dye (P) and of a dyad made of P and a methyl viologen derivative (P-MV), in ethanol-water solutions. In homo-aggregate assemblies of P, the π-π* fluorescence of the isolated chromophore is replaced by excimer emission at lower energy, with a lifetime of 900 ps, due to excimer formation from the initially prepared excitons. In homo-aggregate assemblies of P-MV, photoinduced charge separation, with formation of P+ -MV- species, occurs in 3 ps with a charge recombination of 20 ps. In hetero-aggregate P/P-MV systems, the light energy absorbed by the P components delocalizes over various P subunits, and when a P-MV unit is reached, charge separation occurs; however, excimer emission is present for P/P-MV ratio larger than 3 : 1, indicating that delocalized excitons within the hetero-aggregate systems extend over a limited number of P chromophores.

Perylenes, Porphyrins, and Other Large Dye Molecules for Molecular Layer Deposition

AbstractMolecular layer deposition (MLD) is an incredibly powerful and flexible tool for designing completely new materials with novel and unique properties. The low temperature layer‐by‐layer approach and the use of highly reactive reactants allows one to combine vastly different organic and inorganic species and construct nanostructures with subnanometer precision. If not limited by the volatility of the reactants involved, the possibilities will be endless. This is most notable for the organic building blocks where an overall low volatility severely limits the toolbox of large molecules with interesting optical and electrical properties such as red‐ox activity and optical conversion. In this work, different strategies for molecular design of large molecules are investigated that allow vaporization while still having the necessary reactivity for MLD growth. Using these strategies, film growth with perylene and porphyrin derivatives, both molecules well known for their functional and optical properties are successfully achieved. With this knowledge, there is an opening to include much larger and more complex organic molecules into the world of vapor phase chemistry.

N = 8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility.

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low bandgap (< 1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV-vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives (1 and 2) as subunits of 8-AGNR, with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR. The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical bandgap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm2 V-1 s-1 for the 8-AGNR.

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility**

AbstractStructurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (&lt;1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8‐AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor‐made polymer precursor into 8‐AGNRs was validated by FT‐IR, Raman, and UV/Vis‐near‐infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4‐ghi]perylene derivatives (1 and 2) as subunits of 8‐AGNR, with a width of 0.86 nm as suggested by the X‐ray single crystal analysis. Low‐temperature scanning tunneling microscopy (STM) and solid‐state NMR analyses provided further structural support for 8‐AGNR. The resulting 8‐AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical‐pump TeraHertz‐probe spectroscopy revealed charge‐carrier mobility in the dc limit of ∼270 cm2 V−1 s−1 for the 8‐AGNR.

Crystal-structure simulation of methylthiolated peri-condensed polycyclic aromatic hydrocarbons for identifying promising molecular semiconductors: discovery of 1,3,8,10-tetrakis(methylthio)peropyrene showing ultrahigh mobility.

The crystal structures of molecular semiconductors critically affect their carrier transport properties. One of the promising crystal structures that afford high carrier mobility is a brickwork structure recently reported for 1,3,6,8-tetrakis(methylthio)pyrene (MT-pyrene) showing ultrahigh mobility. However, such ultrahigh mobility was not realized in other methylchalocogenated pyrenes, owing to subtle differences in the molecular positions in their crystal structures. This means that, for developing superior molecular semiconductors, it is desirable to simulate the crystal structure with sufficient quality before time-consuming and labor-intensive synthetic trials. To realize this, we developed a new computational approach to simulating crystal structures of all methylchalocogenated pyrenes, which was then applied to MT-pyrene-related methylthiolated peri-condensed polycyclic aromatic hydrocarbons including perylene, peropyrene, and terrylene derivatives. Among these, 1,3,8,10-tetrakis(methylthio)peropyrene (MT-peropyrene) was expected to show high mobility based on the simulated crystal structures. We thus chose MT-peropyrene as the synthetic target and developed a new peropyrene synthesis method. Thus synthesized MT-peropyrene has virtually the same crystal structure as the simulated one, and its single-crystal field-effect transistors showed mobility as high as 30 cm2 V-1 s-1 and band-like transport behaviors. These results indicate that the present crystal-structure simulation is a powerful tool for exploring promising molecular semiconductors. This article is protected by copyright. All rights reserved.

Excited state dynamics of bay and peri benzothienyl perylene to understand the excimer formation and its dissociation

Many planar acenes such as pyrene, perylene etc. are known to form dimeric complex of their ground and excited state (excimer formation). Relaxation of excimer, carrier mobility & exciton diffusion in the solid state, and even singlet fission depends on the interaction between ground and excited state molecules in excimer. The role of excimer in triplet formation can be understood by: S0↑↓+S1↑↓⇄{S1S01↑↓↑↓}⇄{T1T11↑↑↓↓}⇄T1↑↑+T1↓↓. Intermediate excimer (T1T1)1 formation i.e., (SnS0)1 → (T1T1)1, and its decay to triplets have been studied by several groups, however, reports on the dissociation of excimer are very few. In this work, we aimed to study the dynamics of excimer formation and its further dissociation using perylene derivatives. We synthesized two positional isomers of benzothienyl substituted perylene i.e., peri-BT and bay-BT, and studied their photophysical properties in solution, nanoaggregates, and thermally evaporated thin films. Excited state dynamics in thin films suggest the dissociation of 1(excimer) to a monomeric singlet excited state in a microsecond timescale. Transient absorption spectral characteristics suggest the formation of a charge transfer state within picoseconds, followed by decay to a long-lived (few microseconds) excimer state. The formation of CT is promoted by strong intermolecular interaction in the thin film.

A cross-reactive fluorescent ensemble based on perylene derivative/surfactant assemblies for discrimination of multiple aminoglycoside antibiotics in aqueous solution

Sensitive detection and discrimination of multiple aminoglycosides (AGs) hold paramount importance in the efforts to curtail antibiotic overutilization and to monitor environmental impact. The present work provides a novel discriminative sensor ensemble based on a perylene derivative and SDS assemblies that can recognize nine different aminoglycosides. The fluorescent binary ensemble emits very weak fluorescence due to the strong aggregation of perylene-based probes in SDS pre-micelles. The addition of AGs can induce fast and remarkable fluorescence enhancement. The acquisition of fluorescence variation data at three characteristic emission wavelengths enables the generation of distinctive recognition pattern to each AG. Principal component analysis reveals that the sensor ensemble can correctly identify multiple AGs in both buffered aqueous solution and in 10% human urine. The fluorescence enhancement is attributed to the disaggregation of perylene units caused by the variation of SDS assembly from pre-micelle to micelles resulting from multi-point interaction with AGs. The strategy of modulation effect on fluorescence emission of encapsulated fluorophores by surfactant assemblies has been demonstrated to be highly effective for fabricating single system-based discriminative sensors for aminoglycosides.

Potential-resolved electrochemiluminescence biosensor for simultaneous determination of multiplex miRNA

The multi-target simultaneous detection strategy based on potential-resolved electrochemiluminescence (ECL) has still been a research hotspot in analytical science, but the limited selection of ECL luminophores hinders the development of this field. Herein, polyethyleneimine functionalized perylene derivatives (PTC-PEI) and luminol functionalized gold nanoparticles (Lu–Au NPs) possessed significantly resolved emission potentials as ECL luminophore. The ternary ECL system was constructed with MoS2 nanoflowers and K2S2O8 as the coreaction accelerator and coreactant respectively, which significantly improved the cathode ECL emission of PTC-PEI. Simultaneously, the anode coreaction accelerator ZnO nanoflowers could promote the anode coreactant dissolved O2 reduction, and extremely enhanced the anode ECL emission of Lu–Au NPs. The proposed strategy addressed the major technical challenge of cross interference and competition of the coreactants for dual-biomarker detection, thus enabling accurate detection of miRNA-205 and miRNA-21 from 10 fM to 100 nM, with detection limits of 2.57 and 1.15 fM, respectively. In general, this work achieved a single-step synchronous detection of dual biomarkers, providing a new idea for the ECL detection of multiple biomarkers, and having potential value in the clinical diagnosis.

Tuning the Driving Force for Charge Transfer in Perovskite-Chromophore Systems.

Understanding the interplay between the kinetics and energetics of photophysical processes in perovskite-chromophore hybrid systems is crucial for realizing their potential in optoelectronics, photocatalysis, and light-harvesting applications. By combining steady-state optical characterizations and transient absorption spectroscopy, we have investigated the mechanism of interfacial charge transfer (CT) between colloidal CsPbBr3 nanoplatelets (NPLs) and surface-anchored perylene derivatives and have explored the possibility of controlling the CT rate by tuning the driving force. The CT driving force was tuned systematically by attaching acceptors with different electron affinities and by varying the bandgap of NPLs via thickness-controlled quantum confinement. Our data show that the charge-separated state is formed by selectively exciting either the electron donors or acceptors in the same system. Upon exciting attached acceptors, hole transfer from perylene derivatives to CsPbBr3 NPLs takes place on a picosecond time scale, showing an energetic behavior in line with the Marcus normal regime. Interestingly, such energetic behavior is absent upon exciting the electron donor, suggesting that the dominant CT mechanism is energy transfer followed by ultrafast hole transfer. Our findings not only elucidate the photophysics of perovskite-molecule systems but also provide guidelines for tailoring such hybrid systems for specific applications.