Perylene Diimide Aggregates Research Articles

Tuning Structure and Properties of a Ferromagnetic Organic Semiconductor via a Magnetic Field-Modified Reduction Process

The development of novel synthesis and assembly strategies is critical to achieving a ferromagnetic organic semiconductor with high Curie temperature. In this study, we report a high magnetic field (HMF)-modified solvothermal approach for the reduction in neutral perylene diimide (PDI) into the dianion species to prepare the PDI magnets comprising radical anions after subsequent oxidation processes. The PDI materials, assembled from the dianion solution by an HMF-modified reduction, exhibit a smaller crystallite size and an enlarged distance of the π-π stacking in the PDI aggregates. Furthermore, the PDI magnets obtained from the process under a 9T field reveal weakened ferromagnetism and the rapid degradation of electrical conductivity compared to those prepared without a magnetic field. Based on spectral and structural characterizations, such performance deterioration originates from the enhanced instability of the radical anions exposed to air, as well as the decreased crystallinity for the radical PDIs synthesized from the HMF-modified reduction process. This work demonstrates that magnetic fields offer an effective way in the material synthesis process to manipulate the structure and magnetic properties of the radical-based organic magnets.

An enzyme-propelled target recycling amplification in combination with broad-spectrum quencher aggregated perylene for multiple MicroRNA detection

MicroRNA (miRNA) are regarded as remarkable biomarkers for quick and non-invasive disease diagnosis. In this study, an enzyme-propelled target recycling amplification in combination with DNA/microRNA double strands and perylene diimide (PDI) broad-spectrum quencher was constructed for the determination of multiple miRNAs. The PDI aggregates can be highly efficient in quenching the RNA/DNA and DNA-labeled fluorophores from visible to near-infrared wavelength with quenching efficiencies of over 98 %. The broad-spectrum quenchers can be then employed to establish a multicolor miRNA sensing system by using a label-free approach. In the presence of miRNA, with the help of enzyme, the target recycling was initiated, resulting in the enhancement of fluorescence. The proposed method was highly sensitive to miRNA-21, miRNA-141 and miRNA-155, and the limit of detection obtained was 2.66 fM, 1.33 fM and 1 fM, respectively. Simultaneous and multiplexed detection of various miRNAs in a homogeneous solution was also accomplished. The sensor was used for the determination of miRNA content in human serum samples and the results obtained were satisfactory.

Exciton annihilation in molecular aggregates suppressed through quantum interference.

Exciton-exciton annihilation (EEA), an important loss channel in optoelectronic devices and photosynthetic complexes, has conventionally been assumed to be an incoherent, diffusion-limited process. Here we challenge this assumption by experimentally demonstrating the ability to control EEA in molecular aggregates using the quantum phase relationships of excitons. We employed time-resolved photoluminescence microscopy to independently determine exciton diffusion constants and annihilation rates in two substituted perylene diimide aggregates featuring contrasting excitonic phase envelopes. Low-temperature EEA rates were found to differ by more than two orders of magnitude for the two compounds, despite comparable diffusion constants. Simulated rates based on a microscopic theory, in excellent agreement with experiments, rationalize this EEA behaviour based on quantum interference arising from the presence or absence of spatial phase oscillations of delocalized excitons. These results offer an approach for designing molecular materials using quantum interference where low annihilation can coexist with high exciton concentrations and mobilities.

Aggregation of Charge Acceptors on Nanocrystal Surfaces Alters Rates of Photoinduced Electron Transfer.

Semiconductor nanocrystals (NCs) interfaced with molecular ligands that function as charge and energy acceptors are an emerging platform for the design of light-harvesting, photon-upconverting, and photocatalytic materials. However, NC systems explored for these applications often feature high concentrations of bound acceptor ligands, which can lead to ligand-ligand interactions that may alter each system's ability to undergo charge and energy transfer. Here, we demonstrate that aggregation of acceptor ligands impacts the rate of photoinduced NC-to-ligand charge transfer between lead(II) sulfide (PbS) NCs and perylenediimide (PDI) electron acceptors. As the concentration of PDI acceptors is increased, we find the average electron transfer rate from PbS to PDI ligands decreases by nearly an order of magnitude. The electron transfer rate slowdown with increasing PDI concentration correlates strongly with the appearance of PDI aggregates in steady-state absorption spectra. Electronic structure calculations and molecular dynamics (MD) simulations suggest PDI aggregation slows the rate of electron transfer by reducing orbital overlap between PbS charge donors and PDI charge acceptors. While we find aggregation slows electron transfer in this system, the computational models we employ predict ligand aggregation could also be used to speed electron transfer by producing delocalized states that exhibit improved NC-molecule electronic coupling and energy alignment with NC conduction band states. Our results demonstrate that ligand aggregation can alter rates of photoinduced electron transfer between NCs and organic acceptor ligands and should be considered when designing hybrid NC:molecule systems for charge separation.

Efficient Photoredox Cycles to Control Perylenediimide Self-Assembly.

Photoreduction of perylenediimide (PDI) derivatives has been widely studied for use in photocatalysis, hydrogen evolution, photo-responsive gels, and organic semiconductors. Upon light irradiation, the radical anion (PDI⋅- ) can readily be obtained, whereas further reduction to the dianion (PDI2- ) is rare. Here we show that full 2-electron photoreduction can be achieved using UVC light: 1) in anaerobic conditions by 'direct photoreduction' of PDI aggregates, or 2) by 'indirect photoreduction' in aerobic conditions due to acetone ketyl radicals. The latter strategy is also efficient for other dyes, such as naphthalenediimide (NDI) and methylviologen (MV2+ ). Efficient photoreduction on the minute time-scale using simple LED light in aerobic conditions is attractive for use in dissipative light-driven systems and materials.

Impact of Charge-Resonance Excitations on CT-Mediated J-Type Aggregation in Singlet and Triplet Exciton States of Perylene Di-Imide Aggregates: A TDDFT Investigation

The modulation of intermolecular interactions upon aggregation induces changes in excited state properties of organic molecules that can be detrimental for some optoelectronic applications but can be exploited for others. The time-dependent density functional theory (TDDFT) is a cost-effective approach to determining the exciton states of molecular aggregates, and it has been shown to provide reliable results when coupled with the appropriate choice of the functional. Here we apply a general procedure to analyze the aggregates’ exciton states derived from TDDFT calculations in terms of diabatic states chosen to coincide with local (LE) and charge-transfer (CT) excitations within a restricted orbital space. We apply the approach to study energy profiles, interstate couplings, and the charge-transfer character of singlet and triplet exciton states of perylene di-imide aggregates (PDI). We focus on the intermolecular displacement along the longitudinal translation coordinate, which mimics different amounts of slip-stacking observed in PDI crystals. The analysis, in terms of symmetry-adapted Frenkel excitations (FE) and charge-resonance (CR) states and their interactions, discloses how the interchange of the H/J character for small longitudinal shifts, previously reported for singlet exciton states, also occurs for triplet excitons.

Singlet Fission Dynamics of Colloidal Nanoparticles of a Perylenediimide Derivative in Solutions.

Singlet fission (SF) is an intriguing process in which a singlet exciton produces two triplet excitons in molecular aggregates. Perylenediimide (PDI) derivatives are promising materials for SF-based photovoltaics, and the SF process in PDI aggregates is important to investigate for their applications. In this work, we studied the entire SF process occurring in the colloidal nanoparticles of a PDI derivative in solutions by using time-resolved fluorescence and transient absorption (TA) experiments. PE-PDI was found to form the colloidal nanoparticles of H- and J-aggregates in polar solvents. The TA signals of PE-PDI aggregates in solutions were selectively measured by wavelength-dependent excitation. The TA signals were analyzed by using a global fitting analysis, and all kinetic parameters involved in the entire SF process were determined. Our current investigation has confirmed that fast SF occurs on the surface of the colloidal nanoparticles of PDI aggregates via the charge transfer mediated mechanism, giving a high quantum yield of triplet excitons.

Enhancement of visible light driven dye degradation and photocatalytic H2 evolution over MoS2 through combination with perylene diimide aggregates

The incorporation of PPDI MBs into MoS2 NFs changes the nature of their edge, increases the driving force to effectively separate and transfer the photogenerated charge carriers, and improves the overall photocatalytic performance of the material.

Cover Feature: Improving the Quantum Yields of Perylene Diimide Aggregates by Increasing Molecular Hydrophobicity in Polar Media (ChemPhysChem 18/2017)

Cover Feature: Improving the Quantum Yields of Perylene Diimide Aggregates by Increasing Molecular Hydrophobicity in Polar Media (ChemPhysChem 18/2017)

Improving the Quantum Yields of Perylene Diimide Aggregates by Increasing Molecular Hydrophobicity in Polar Media.

Here we report the quantum yield of four aggregated perylene diimide (PDI) species that vary by the length of the branched side chains attached at the N,N' imide positions. The PDI molecules were dissolved in binary water:methanol solvents as a means to vary the solvent polarity and control the degree of aggregation in solution. By performing spectroscopy, kinetics, and light scattering experiments, the nature of the molecular interactions in the solutions was determined. The maximum quantum yield of the aggregated molecules increased from 0.04 for the shortest chain molecule (B2) to 0.20 for the largest chain molecule (B13). The higher quantum yield of B13 compared with B2 correlates well with an increase in the fluorescence lifetime. The monomer emission lifetime was 4.8 ns whereas a lifetime as high as 21.2 ns was measured for the B13 aggregate fluorescence. A shorter sub-nanosecond lifetime was also measured for suspended colloids in B5, B9, and B13. The enhanced quantum yield is attributed to an increase of disorder in the B13 aggregates. As the polarity of the solution increases, the hydrophobic effect further enhances the disorder, and, therefore, the quantum yields in these particles.

Perylene Diimide Aggregates on Sb-Doped SnO2: Charge Transfer Dynamics Relevant to Solar Fuel Generation

The deposition of perylene diimide-based aggregates (PDI) onto wide band gap n-type Sb-doped SnO2 (ATO) was investigated with the aim of finding efficient and versatile dye-sensitized platforms for photoelectrochemical solar fuel generation. These ATO-PDI photoanodes displayed hydrolytic stability in a wide range of pH (from 1 to 13) and revealed superior performances (up to 1 mA/cm2 net photocurrent at 1 V vs SCE) compared to both WO3-PDI and undoped SnO2-PDI when used in a photoelectrochemical setup for HBr splitting. Although ATO, SnO2, and WO3 are endowed with similar conduction band edge energetics, in ATO the presence of a significant density of intrabandgap states, whose occupancy varies with the applied potential, plays a substantial role in tuning the efficiency of photoinduced charge separation and collection. Furthermore, the investigation of the charge injection kinetics confirmed that, even in the absence of applied bias, ATO and WO3 are the best substrates for the oxidative quenching of poor...

Photoinduced charge-transfer dynamics simulations in noncovalently bonded molecular aggregates.

The rational design of new materials as prototype systems for organic solar cells remains challenging. Perylene diimide has emerged as a promising material to replace fullerene derivatives because of its synthetic flexibility, leading to the manipulation of their optical properties. As a result of their fused aromatic core that favors π-π stacking interactions, the aggregation of these molecules can reach highly ordered nanostructures as one-dimensional nanofibers, with a fast photoinduced charge transfer mechanism. In this article, we present an atomistic description of the photoexcited exciton dynamics in noncovalently bonded perylene diimides by time integration of the electron density in the presence of external time varying electric fields. We show that our approach is able to capture and explain the physics that underlies the charge transport mechanism through perylene diimide aggregates.

Enhancement of visible-light-driven photocatalytic H2 evolution from water over g-C3N4 through combination with perylene diimide aggregates

Graphitic carbon nitride (g-C3N4) is among the most promising metal-free photocatalysts for H2 production from solar-driven water reduction. However, the photocatalytic efficiency of bulk g-C3N4 powders is limited. In this work, molecular aggregates of perylene tetracarboxylic diimides (PTCDIs, a robust class of air-stable n-type organic semiconductor) were loaded via solution processing on the surface of g-C3N4, which is pre-deposited with cocatalyst Pt nanoparticles. The PTCDIs/Pt/g-C3N4 composites thus fabricated exhibit broader visible-light response than Pt/g-C3N4, and possess excellent photochemical stability. The initial intramolecular charge transfer features of the PTCDIs, as well as their energy levels being matched to g-C3N4, ensure subsequent charge separation in the PTCDIs/Pt/g-C3N4 composites. When the composites are dispersed into aqueous solutions containing triethanolamine as a sacrificial electron donor, a tenfold enhancement of H2 evolution activity (∼0.375μmolh−1) is achieved compared to bare Pt/g-C3N4 under visible-light (λ≥420nm) irradiation.

On the role of aggregation effects in the performance of perylene-diimide based solar cells

A model bulk-heterojunction of a perylene diimide (PDI) monomeric derivative is studied for interrogating the role of PDI aggregates in the photocurrent generation efficiency (ηPC) of PDI-based organic photovoltaic (OPV) devices. Blend films of the PDI derivative and the poly(indenofluorene) (PIF) polymer annealed between room temperature and 220°C, are used as the photoactive layers for the fabrication of OPVs. The positive effect of thermal annealing is assigned to the evolution of PDI aggregates in the amorphous PIF matrix. Annealing increases the electron mobility by three orders of magnitude. In contrast, owned to the thermally inert PIF matrix used, hole mobility increases only by a factor of six. High resolution cross-sectional scanning electron microscopy suggests that ηPC in PDI-based OPVs is not limited by the PDI aggregates but by their improper alignment. In situ Raman spectra and density functional theory calculations identify a marker for monitoring the strength of π–π stacking interactions between PDI monomers. It s further demonstrated that the electron-collecting electrode of the PIF:PDI devices dictates their performance. The use of Al is found to impede charge extraction and this is attributed to an unidentified product of the reaction between PDI and Al that leads to the formation of an electron-blocking layer. Device performance rectifies when a Ca/Al electrode is used and the power conversion efficiency is increased by a factor of four.

The effect of perylene diimide aggregation on the light collection efficiency of luminescent concentrators

The effect of dye concentration on the efficiency of a luminescent concentrator based on a perylene diimide (PDI) derivative incorporated in poly(methyl methacrylate) films cast on glass substrates is described. The predictions of ray-trace modelling are compared to experimental data from integrating sphere luminescence measurements. Increasing the PDI concentration leads to aggregation of the dye and an associated shift in the emission spectrum. The larger Stokes shift between emission and absorption spectra of the aggregated form reduces luminescence re-absorption and increases collection efficiency. However, the lower fluorescence quantum yield of the PDI aggregates restricts overall absorbed light to luminescence conversion. The relevance of the results to optimize organic molecule based luminescent solar concentrators is discussed.

A Turn-on Fluorescent Sensor for Pyrophosphate Based on the Disassembly of Cu2+-Mediated Perylene Diimide Aggregates

A complex between an anionic perylene diimide derivative (PDI-GlyAsp) and cupric ion has been prepared and applied to be turn-on fluorescent probe for the detection of pyrophosphate (PPi) in 100% aqueous solution. The complex formation process and PPi detection have been studied by absorption and emission spectroscopy. It was confirmed that the introduction of cupric ion into PDI-GlyAsp solution resulted in the assembly of PDI-GlyAsp into PDI-GlyAsp/Cu(2+) aggregates, leading to the fluorescence quenching of PDI-GlyAsp. Upon addition of PPi into the above solution led to the disassembly of the aggregates due to the competitive binding of PPi with Cu(2+) in the PDI-GlyAsp/Cu(2+) complex, and a recovery of PDI-GlyAsp emission was observed. Therefore, the PDI-GlyAsp/Cu(2+) complex can be applied as a turn-on fluorescent probe for detecting PPi with high selectivity and sensitivity.

Energy and Electron Transfer in a Poly(fluorene-alt-phenylene) Bearing Perylenediimides as Pendant Electron Acceptor Groups

We describe the synthesis and characterization of a novel poly(fluorene-alt-phenylene) substituted with perylenediimide (PDI) moieties as pendant groups. Cyclic voltammetry experiments show the amphoteric nature of the material, which combines the good electron donor ability of the polymeric chain with the acceptor properties of the pendant PDI moieties. Absorption spectroscopy suggests the presence of PDI aggregates, whereas the emission spectra show a strong emission quenching of both the polymeric backbone and the PDI units. Further investigation on the energy and/or electron-transfer processes involved is carried out by temperature-dependent excitation spectra and photoluminescence lifetimes. These studies show the presence of electron transfer not only from the electron donor polymeric chain to the pendant PDI units but also, and more remarkably, to PDI aggregates both in solution and in solid state, as is further confirmed by photoinduced absorption spectroscopy.

Molecular aggregate formation and microphase segregation effects on the photoelectrical and photovoltaic properties of polyimide-perylenediimide composite films

The strong increase of electrophotographic sensitivity, charge carrier photogeneration quantum yield and improved photovoltaic characteristics (sandwich cells with ITO, Al electrodes) are found for films of photoconductive soluble polyimides based on doubled triphenylamine heavily doped by the soluble perylenediimides (with content up to 50-60% wt). It is shown that the effect is due to perylenediimide aggregates of some tens nanometers size which are formed during the film casting at high solvent evaporation rate. The further increase of photoelectric and photovoltaic parameters is achieved by using the films of polymer blends of polyimides with polyetherimides (Ultem-1000 type) also doped with soluble perylenediimides. In this case the effect is due to microphase segregation in doped polymer blend films caused by the partial incompatibility of polymers, that results in the formation of microregions with n- and p-types of photoconductivity contacting with each other and possible appearance of p-n bulk microheterojunctions.