Acid Diimide Research Articles

Graphene decorated with Pd nanoparticles via electrostatic self-assembly: A highly active alcohol oxidation electrocatalyst

Graphene nanosheets (GS) are non-covalently functionalized with novel N,N-bis-(n-butylimidazolium bromide salt)-3,4,9,10-perylene tetracarboxylic acid diimide (PTCDI-ILs) via the π–π stacking, and then employed as the support of Pd nanoparticles. The negatively charged Pd precursors are adsorbed on positively charged imidazolium ring moiety of PTCDI-ILs wrapping GS surface via electrostatic self-assembly and then in situ reduced by NaBH4. X-ray diffraction and transmission electron microscope images reveal that Pd nanoparticles with an average size of 2.7nm are uniformly dispersed on GS surface. The Pd/PTCDI-ILs/GS exhibits unexpectedly high activity toward alcohol oxidation reaction, which can be attributed to the large electrochemical surface area of Pd nanoparticles. It also shows enhanced electrochemical stability due to the structural integrity of PTCDI-ILs/GS. This provides a facile approach to synthesize GS-based nanoelectrocatalysts.

Perylene diimide: Synthesis, fabrication and temperature dependent electrical characterization of heterojunction with p-silicon

A novel, n-type, organic semiconductor N-Butyl-N′-(6-hydroxyhexyl)perylene-3,4,9,10-tetracarboxylic acid diimide (N-BuHHPDI) has been successfully synthesized in high yield. The compound has been characterized by atomic force microscopy (AFM) to understand the morphological properties of a new n-type organic semiconducting material. A 120nm thin film of N-BuHHPDI has been sandwiched between Al and p-Si to form Al/N-BuHHPDI/p-Si device using the vacuum thermal evaporation technique. The electrical properties of sandwich type Al/N-BuHHPDI/p-Si device have been investigated. The current voltage (I–V) characteristics of the device, in dark, have been measured in the temperature range of 300–330K. At room temperature, the device exhibits rectifying behavior with a rectification ratio of 51.5 at ±6.8V. The device parameters such as ideality factor, barrier height, series and shunt resistances have been extracted using the conventional I–V characterization method. The effect of temperature on these parameters is also studied. Alternative electrical characterization methods such as Cheung's functions and Norde's techniques have been employed to measure the device parameters for comparison. The conduction mechanisms are investigated through the interface of N-BuHHPDI and p-Si.

Bis-thioether-Substituted Perylene Diimides: Structural, Electrochemical, and Spectroelectrochemical Properties

The synthesis and separation of the 1,6- and 1,7- isomers of N,N'-bis(alkyl)diadamantylthio-3,4,9,10-perylenetetracarboxylic acid diimide are reported. Investigations of the structural, electrochemical, spectroscopic, and spectroelectrochemical properties of the isomers reveal a sequence of electrochemically and chemically reversible reduction processes for both isomers. Three X-ray crystal structures are reported including a pair of 1,6- and 1,7-isomers demonstrating the twist of the perylene core in the solid state. Our studies thoroughly characterize the mono- and direduced states of the two isomers allowing unequivocal characterization of the reduced species by UV-vis and IR spectroscopic measurements. EPR studies also allow direct identification of the monoreduced PTCDI species and spectroscopic measurements confirm the delocalization of electronic density around the carbonyl moieties of the reduced species.

Perylene diimides based materials for organic solar cells

Abstract Perylene-3,4,9,10-tetracarboxylic acid diimides (PDIs) and their derivatives represent one of the most promising class of electron accepting materials, due to their outstanding chemical and physical properties, including high electron mobility and high molar absorption coefficients. Their rigid, fused aromatic core favours π–π intermolecular interactions imparting n-type semiconducting properties useful for optoelectronic applications. The PDIs have attracted interest as photovoltaic functional materials for their strong electron-accepting character and significant charge transport properties. This feature article describes the application of PDI based molecules and polymers in organic photovoltaic solar cells.

Comparative study of soluble naphthalene diimide derivatives bearing long alkyl chains as n-type organic thin-film transistor materials

In this study, several naphthalene tetracarboxylic acid diimide (NTCDI) derivatives substituted at the N and N′ positions with long normal alkyl chains of different lengths were evaluated as soluble n-type organic thin-film transistor (TFT) materials. NTCDI derivatives with diundecyl (NTCDI-C11), didodecyl (NTCDI-C12), and ditridecyl (NTCDI-C13) exhibited acceptable solubility in chloroform, and their TFTs showed typical n-type TFT performance with relatively high field effect electron mobility (∼0.2cm2/Vs) after annealing at a workable temperature of 150°C. Although NTCDI with dioctyl (NTCDI-C8) showed good solubility in chloroform, the TFT performance of this material was highly inferior to that of NTCDI-C11, NTCDI-C12, or NTCDI-C13. We could not anneal NTCDI-C8 thin films at workable temperatures in vacuo because of sublimation of the material from the substrates. In contrast, NTCDI with dipentadecyl (NTCDI-C15) and dioctadecyl (NTCDI-C18) exhibited both poor solubility for chloroform and poor TFT performance. In short, these compounds are not suitable as soluble n-type organic TFT materials.

New organic–inorganic hybrid materials based on perylene diimide–polyhedral oligomeric silsesquioxane dyes with reduced quenching of the emission in the solid state

Abstract Solid state luminescent materials are the subject of ever growing interest both from a scientific and a technological point of view because high-tech applications of light emitting materials very often require their use in the condensed phase. Aggregation caused quenching processes however represent an obstacle to the development of most luminogens in the condensed phase. This is why particularly fascinating are those materials showing high emission intensity in the solid state. Aggregation caused quenching is particularly detrimental for π-extended polycyclic aromatic hydrocarbons, for example perylene tetracarboxylic acid diimides which are characterized by a near-unity fluorescence quantum yield in solution but are far less emissive in the solid state. Here we report on the easy preparation and on the optical investigation of perylene tetracarboxylic acid diimide derivatives linked to the inorganic cage of polyhedral oligomeric silsesquioxanes. These new hybrid perylene diimide–polyhedral oligomeric silsesquioxane dyes show in solution the typical absorption and emission features of the perylene diimide fragment, with a quantum efficiency close to unity. Moreover, in the solid state (both as spin-coated films and powders) the electronic absorption spectra indicate a reduced fluorophore aggregation and significant quantum yield efficiencies induced by the positive effect of the polyhedral oligomeric silsesquioxane cage.

DNA Triplex‐Mediated Assembly of Polyaromatic Chromophores

The synthesis and characterization of intramolecular triple-helical DNA structures containing polyaromatic pyrene and perylene (perylenetetracarboxylic acid diimide, PDI) building blocks are presented. Two 1,8-dialkynylpyrene units are located in the Watson-Crick stem of the construct, while a PDI or a natural thymidine is present in the Hoogsteen strand. The triple helical structures were investigated by UV/VIS absorbance, fluorescence spectroscopy, and circular dichroism (CD) measurements. The folding of the intramolecular triple helix can be monitored by changes in the vibronic transition ratios, as well as by a change in the alkynylpyrene fluorescence (monomer vs. excimer). It is shown that thymine in the third strand has a pronounced influence on the interaction and, thus, on the fluorescence properties of two pyrene building blocks.

Synthesis and Aggregation Properties of Polycationic Perylenetetracarboxylic Acid Diimides

AbstractThe synthesis and structural characterization of a first family of dendronized polycationic perylenetetracarboxylic acid diimides (PDIs) 7, 8, and 10 is reported. They were obtained by amide coupling reactions of pyridinium salt head groups with terminal carboxylic groups of Newkome‐dendron‐type functionalized PDIs. Resulting pyridinium‐terminated PDIs 7, 8, and 10 are highly water‐soluble, independent of the pH value. This is due to 6, 18, and 9 permanent positive charges, respectively. PDIs 7 containing the smaller first‐generation dendrons exhibit a pronounced aggregation behavior in water. This was studied by absorption and fluorescence spectroscopy, by pulsed‐gradient spin‐echo (PGSE, DOSY) NMR measurements, and by cryo‐transmission electron microscopy (cryo‐TEM). The counterparts containing the bulkier second‐generation dendrons hamper aggregation, and as a consequence intermolecular π–π stacking interactions between the perylene cores is suppressed.

In Situ Monitoring Alzheimer's Disease β‐Amyloid Aggregation and Screening of Aβ Inhibitors Using a Perylene Probe

A cationic perylene tetracarboxylic acid diimide derivative (1) is employed as a probe for in situ monitoring of Aβ aggregation and screening Aβ inhibitors. The assay is based on the fluorescence change through the aggregation of compound 1 following Aβ assembly. Importantly, this probe, compared with the well known amyloid-staining compound thioflavin T (ThT), is more sensitive to Aβ oligomer, which is highly toxic and plays a crucial role in the early stages of Alzheimer's disease.

Improving the affinity of naphthalene diimide ligand to telomeric DNA by incorporating Zn2+ ions into its dipicolylamine groups

N,N′-bis[3-[3-(2,2′-dipicolyl)methylaminopropyl]-methylaminopropyl]naphthalene-1,4,5,8-tetracarboxylic acid diimide, 1, and its complex with zinc ions, 2, were investigated against telomeric sequences, [TAGGG(TTAGGG)3] and [AGGG(TTAGGG)3], which reveal different G-quadruplex structures depending on the conditions. Spectrophotometric, SPR, and CD techniques revealed that both ligands showed large binding constants to hybrid-type G-quadruplexes formed in the presence of K+ ions. Moreover, 2 revealed higher affinity to investigated oligonucleotides suggesting that complex of naphthalene diimide derivative with Zn2+, comparing to 1, provided additional electrostatic or coordination interactions between positively charged zinc ions and condensed negative charged phosphate anions from G4 DNA.

Perylene ligand wrapping G-quadruplex DNA for label-free fluorescence potassium recognition

A perylene ligand, N,N-bis-(1-aminopropyl-3-propylimidazol salt)-3,4,9,10-perylene tetracarboxylic acid diimide ligand (PDI), which consisted of π-conjugated perylene moiety and hydrophilic side chains with positively charged imidazole rings, was used to wrap G-quadruplex for fluorescence turn-on K+ recognition. Electrostatic attraction between PDI's positively charged imidazole rings and DNA's negatively charged phosphate backbones enabled PDI to accumulate on DNA. Upon trapping K+, these G-rich DNA sequences transitioned to G-quadruplex. Subsequently, PDI ligands wrapped G-quadruplex, in which the flat aromatic core of PDI ligand interacted with G-quartet through π–π stacking and the side chains were positioned in grooves through electrostatic interactions. Consequently, the interaction mode change and conformational transition from PDI stacked G-sequence to PDI wrapped G-quadruplex led to PDI fluorescence enhancement, which was readily monitored as the detection signal. This strategy excluded the sequence tagging step and exhibited high selectivity and sensitivity towards K+ ion with the linear detection range of 10–150nM. Besides, PDI ligands may hold diagnostic and therapeutic application potentials to human telomere and cancer cells.

Selective isolation of G-quadruplexes by affinity chromatography

G-quadruplex (G4) is a characteristic secondary structure of nucleic acids containing repetitive tandem guanines. G4-forming sequences are found prevalent in the human genome by bioinformatics analysis. Accumulating evidence has suggested that G4s are involved in many biological processes. Selective isolation of G4s would be an effective tool in the study of G4s. In this paper, we prepared four affinity matrixes using hemin or a perylene derivative (N,N′-Bis-(2-(amino)ethyl)-3,4,9,10-perylenetetracarboxylic acid diimide, Pery01) as ligand, and investigated the retention behaviors of different G4s on these matrixes. Our experimental results suggest that the π-π stacking interaction between ligand and G-tetrad plays a key role in the selective isolation of G4s, whereas the electrostatic interaction between DNA and matrix causes the nonspecific binding. One matrix prepared by immobilizing Pery01 on polyglycidylmethacrylate (PGMA) beads through an aminocaproic acid spacer exhibits good selectivity for parallel structure G4s and has been successfully used to directly isolate a spiked parallel G4 from plasma.

PA-PTCDI for use in μc-Si:H Solar Cells: Basic Chemical and Morphological Effects

Basic research on N,N’-diallyl-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic acid diimide (Phenoxy-Allyl- PTCDI, short PA-PTCDI) is presented. Synchrotron photoemission spectroscopy is used in order to investigate a possible chemical interaction of PA-PTCDI on two differently treated silicon substrates. Additional AFM measurements investigate the influence that storage under ambient conditions has on the morphology of thin dye films.

Self-Assembly of a Donor–Acceptor Nanotube. A Strategy To Create Bicontinuous Arrays

The self-assembly of bolaamphiphile 1 into nanotubes containing a nanostructured electron donor/acceptor heterojunction is reported. In 10% MeOH/H(2)O, the tetraphenylporphyrin (TPP) and 1,4,5,8-naphthalenetetracarboxylic acid diimide chromophores engage in strong J-type π-π interactions within monolayer rings that further stack into the nanotube assemblies. In 10% MeOH/H(2)O at pH 1 or 11 or in pure MeOH, assembly is driven exclusively by the TPP ring, leading to the formation of nonspecific, unstructured aggregates. Steady-state, time-resolved fluorescence and femtosecond transient absorption spectroscopy revealed a strong dependence of the fluorescence decay and electron-transfer/charge-recombination time constants on the nature of the assemblies. These studies highlight the importance of local nanostructure in determining the photophysical properties of optoelectronic materials.

Decorated graphene sheets for label-free DNA impedance biosensing

An efficient DNA impedance biosensing platform is constructed, in which positively charged N,N-bis-(1-aminopropyl-3-propylimidazol salt)-3,4,9,10-perylene tetracarboxylic acid diimide (PDI) is anchored to graphene sheets. The π–π stacking and electronic interactions are elucidated by the distinct absorption features in UV–vis spectra and by quenching perylene fluorescence in contact with graphene. The rational design and tailoring of graphene surface invest it with desired properties (dispersive, structural, photoelectrical and conductive, etc.) and boost its application. Electrostatic interaction between PDI’s positively charged imidazole rings and negatively charged phosphate backbones of single-stranded DNA (ssDNA) facilitates ssDNA immobilization. This manner is different from these mainly based on the attraction between the rings in DNA bases and the hexagonal cells of graphene, which is disturbed after hybridization and causes the leaving of formed double-stranded DNA from graphene surface. The electrostatic ssDNA grafting occupies phosphate backbones and particularly leaves the bases available for efficient hybridization. DNA immobilization and hybridization lead to PDI/graphene interfacial property changes, which are monitored by electrochemical impedance spectroscopy and adopted as the analytical signal. The conserved sequence of the pol gene of human immunodeficiency virus 1 is satisfactorily detected via this PDI/graphene platform and shows high reproducibility, selectivity.

Interactions of a platinum-modified perylene derivative with the human telomeric G-quadruplex.

The interactions of a newly synthesized platinum-modified perylene derivative, compound 7 ([{Pt(dien)}(2)(μ-4-S,S')](NO(3))(4) (dien = diethylenetriamine, 4 = N,N'-bis(1-(2-aminoethyl)-1,3-dimethylthiourea)-3,4,9,10-perylenetetracarboxylic acid diimide), with the human telomeric repeat were studied using various model oligo(deoxy)ribonucleotides to mimic the polymorphic nature of the telomeric G-quadruplex. UV/visible spectroscopy, CD spectropolarimetry, electrospray mass spectrometry (ES-MS), and isothermal titration calorimetry (ITC) were used to demonstrate that compound 7 selectively recognizes the antiparallel form of the unimolecular telomeric G-quadruplex formed by the sequence d(TTAGGG)(4) (dG-24), to which it binds with a 2:1 stoichiometry and nanomolar affinity. Compared with telomeric DNA, the first binding event of compound 7 in titrations with the RNA quadruplex formed by r(UUAGGG)(4) (rG-24) is 1 order of magnitude weaker. Compound 7 does not induce the antiparallel G-quadruplex RNA, which invariably exists in a parallel form and dimerizes in solution. On the basis of the cumulative experimental data, two distinct mechanisms are proposed for the recognition of G-quadruplex DNA and RNA by compound 7. Potential biomedical and biochemical applications of the platinum-perylene technology are discussed.

Toward Functional Inorganic/Organic Hybrids: Phenoxy-allyl-PTCDI Synthesis, Experimentally and Theoretically Determined Properties of the Isolated Molecule, Layer Characteristics, and the Interface Formation of Phenoxy-allyl-PTCDI on Si(111):H Determined by SXPS and DFT

A new perylene diimide derivative, namely N,N′-diallyl-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic acid diimide (phenoxy-allyl-PTCDI, abbreviated PA-PTCDI), is introduced. The investigations presented in this paper aim at finding a molecule for use as a sensitzer in thin film silicon solar cells in order to enhance efficiency. The synthesis is described along with optical and electrochemical measurements of PA-PTCDI in solution. A good agreement is found between the measured data and theoretical calculations. The molecule is characterized further by optical and photoemission data on thin films, which also show that the dye can be sublimed in vacuum. The interface between the dye and silicon is investigated on the model system Si(111):H with synchrotron-induced photoemission spectroscopy. The result is an electronic lineup with the gap centers of silicon and PA-PTCDI almost at identical positions and thus very similar band discontinuities from the lowest unoccupied molecular orbital (LUMO) to the conduction band as well as from the highest occupied molecular orbital (HOMO) to the valence band. This clearly permits a transfer of photogenerated electrons and holes from PA-PTCDI to silicon. The experimental valence band discontinuity matches very well the value calculated for a very similar PTCDI molecule.

ChemInform Abstract: Perylene‐3,4,9,10‐tetracarboxylic Acid Diimides: Synthesis, Physical Properties, and Use in Organic Electronics.

AbstractReview: 161 refs.

Zinc(II)‐selective ratiometric fluorescent probe based on perylene bisimide derivative

A fluorescent probe of N,N'-biscyclohexyl-1,7-di(3-pyridoxy)-perylene-3,4:9,10-tetracarboxylic acid diimide has been synthesized, and exhibited excellent selectivity and sensitivity for Zn(2+) over other competing biological cations. The Zn(2+) -selective fluorescence blue-shift and enhancing property in conjunction with a visible colorimetric change from orange to green could be observed. With favorable photophysical properties in the visible region, the perylene bisimide derivatives remarkably improved the performance of the probe.

Perylene-3,4,9,10-tetracarboxylic Acid Diimides: Synthesis, Physical Properties, and Use in Organic Electronics

Perylene-3,4,9,10-tetracarboxylic acid diimides (perylene diimides, PDIs) have been used as industrial pigments for many years. More recently, new applications for PDI derivatives have emerged in areas including organic photovoltaic devices and field-effect transistors. This Perspective discusses the synthesis and physical properties of PDI derivatives and their applications in organic electronics.