Bisimide Derivatives Research Articles

Ambipolar organic thin film transistors prepared with a one step solution technique

One of the most challenging problems limiting the development of the technology of organic electronics is a lack of simple, solution based, techniques for producing organic thin film transistors (OTFTs) with ambipolar characteristics. In this work, a simple method of manufacturing ambipolar OTFTs, based on a zone-casting technique, is presented. This technique was used to prepare thin and highly oriented films from a combination of the p-type organic semiconductor, TIPS-Pentacene, with one of the two naphthalene bisimide derivatives, both exhibiting electron conductivity. The OTFTs produced with such active layers display ambipolar properties with symmetric characteristics and electron and hole mobility in the best case amounting to: μe=1.5×10−2 and μh=1.1×10−2cm2V−1s−1, respectively.

Effect of Triplet State on the Lifetime of Charge Separation in Ambipolar D-A1-A2 Organic Semiconductors

An ambipolar organic semiconductor with styrene based triphenylamine derivative (MTPA) as an electron donor (D), triazine group (TRC) as an electron acceptor (A1), and 9,10-anthraquinone (AEAQ) as a second electron acceptor (A2) has shown an 8-fold increase in the lifetime of charge separation with a high performance as solar cell materials with respect to the D-A1 architecture and demonstrated a general D-A1-A2 architecture as a promising materials design strategy for photovoltaics. Here we synthesized and characterized two new D-A1-A2 compounds with perylene bisimide derivatives (PDI and PBI) as A2 using an integrated experimental and computational method to study and compare the kinetics of three MTPA-TRC-A2 systems. A two-step sequential decay pathway was observed in both MTPA-TRC-PDI and MTPA-TRC-PBI but a direct decay pathway in MTPA-TRC-AEAQ. The charge separated state with a lifetime of 22 ns in the PDI system and 75 ns in the PBI system relaxes to the corresponding triplet state followed by the d...

Intramolecular Charge-Transfer Interaction of Donor–Acceptor–Donor Arrays Based on Anthracene Bisimide

We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

A perylene bisimide derivative with pyrene and cholesterol as modifying structures: synthesis and fluorescence behavior.

A perylene bisimide (PBI) derivative (C-PBI-Py) of pyrene (Py) and cholesteryl residue (C) possessing intra-molecular energy transfer properties and three reference compounds (C-Py, C-PBI, PBI-Py) were designed and synthesized, where C was introduced in order to enhance the solubility of the relevant compounds in organic solvents. UV-vis absorption, steady-state fluorescence, cyclic voltammetric and theoretical calculation studies revealed that: (1) the PBI unit and Py moiety of C-PBI-Py could act as two individual chromophores, (2) the excited state energy of Py could transfer to PBI within a single molecule of the compound, and (3) the PBI moiety of the compound tends to form aggregates and shows PBI excimer emission. Time-resolved and temperature-dependent emission spectroscopy studies revealed the presence of both H-type excimer and J-type excimer, and formation of them via either the Birks' scheme or the pre-formed scheme due to strong π-π stacking that was elucidated by concentration-dependent (1)H NMR spectroscopy measurement. In addition, the studies also indicated that the energy transfer occurs via an electron exchange mechanism (Dexter scheme). Results of this study will be useful in the development of new solvatochromic and other environment-sensitive fluorophores based on alteration of intra-molecular energy transfer efficiency.

Supramolecular ensemble of PBI derivative and copper nanoparticles: a light harvesting antenna for photocatalytic C(sp2)–H functionalization

A supramolecular ensemble of triazole-appended perylene bisimide (PBI) derivative 4 and in situ generated copper nanoparticles (CuNPs) serves as a light-harvesting antenna in photocatalytic C(sp2)–H alkynylation and amination reactions of arenes under mild and eco-friendly conditions.

ChemInform Abstract: Aggregates of Perylene Bisimide Stabilized Superparamagnetic Fe3O4 Nanoparticles: An Efficient Catalyst for the Preparation of Propargylamines and Quinolines via C—H Activation.

AbstractAggregates of the perylene bisimide derivatives act as reactors and stabilizers for the preparation of superparamagnetic Fe3O4 nanoparticles.

A perylene bisimide derivative with a LUMO level of −4.56 eV for non-fullerene solar cells

Conjugated polymers with LUMO levels of −4.00 eV combined with a newly designed perylene bisimide compound with a LUMO level of −4.56 eV were found to have efficient charge transfer and provide power conversion efficiencies up to 1.4% in solar cells.

A liquid-crystalline perylene tetracarboxylic bisimide derivative bearing trisiloxan-2-yl moieties: influence on mesomorphic properties and electron transport

Mesomorphic and electron transport properties are compared for liquid-crystalline perylene tetracarboxylic bisimide derivatives bearing linear disiloxane and trisiloxane chains, as well as trisiloxan-2-yl groups.

Fabrication of a new fluorescent film and its superior sensing performance to N-methamphetamine in vapor phase

A super-sensitive fluorescent film for N-methamphetamine (MAPA), one of the most widely abused drugs throughout the world, was designed and fabricated. The film was realized through the self-assembly of a newly developed fluorescent compound, PDC, onto a glass plate surface, where PDC is a rational combination of a new perylene bisimide derivative and cholesterol. The film as prepared exhibits unprecedented sensing performances: (1) the film is super-sensitive to the presence of either N-methyl-phenethylamine (MPEA, a simulant of MAPA) or MAPA in vapor state, and the detection limit (DL) of MPEA is ∼5.5ppb, a lowest value in vapor state detection reported till now, (2) the presence of potential interferences (amines, organic solvents, water, apple pomace and etc) shows little effect on MAPA sensing, (3) the sensing process is highly fast and fully reversible. Moreover, the film as developed is photo-chemically stable. Based on this favorable film, a conceptual MAPA detector for practical application was successfully developed and presented.

Photorefractivity of Perylene Bisimide‐Sensitized Poly(4‐(diphenylamino)benzyl acrylate)

A perylene bisimide derivative of N,N′‐diisopropylphenyl‐1,6,7,12‐tetrachloroperylene‐3,4,9,10‐tetracarboxyl bisimide (PBI) is synthesized and used as a sensitizer for a photorefractive (PR) polymer composite. Small amount (0.1 wt%) of PBI sensitizer gives the maximum PR performance of composite based on poly(4‐(diphenylamino)benzyl acrylate) (PDAA) (45 wt%), 2‐(4‐(azepan‐1‐yl)benzylidene)malononitrile (35 wt%), and (4‐(diphenylamino)phenyl)methanol (24.9 wt%). High external diffraction efficiency of 49%, response time of 47 ms, and sensitivity of 28 cm2 J−1 are obtained under an applied electric field of 40 V μm−1 at writing beam of 532 nm. PBI sensitizer effectively forms a charge‐transfer complex with PDAA, which favors the generation of the charge carriers followed by the space‐charge formation. Furthermore, low PBI concentration contributes to low absorption coefficient at 532 nm, which leads to better PR performance. image

A supramolecular helix that disregards chirality.

The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks.

Formation of An Ionic PTCA-β-CDNH2Complex and Its Application for Phenol Sensing in Aqueous Phase

On the basis of proton transfer in aqueous phase, we prepared a water-soluble and highly fluorescent ionic complex of 3,4,9,10-perylene tetracarboxylic acid (PTCA) and 6-deoxy-6-amino-β-CD (β-CDNH2) and studied its fluorescence behavior. It was found that the fluorescence emission of the complex is sensitive and selective to the presence of trace amount of toxic phenolic compounds, in particular phenol, which is crucial for water quality control. The detection limit (DL) of the method to the analyte is ~0.03 μM, a lowest value reported in literatures for similar techniques. Interestingly, the detection at an unprecedented subnanogram (DL, ~0.12 ng/cm(2)) level can also be conducted in a visualized manner, which may provide a simple and low-cost protocol for on-site and real-time detection of the analyte. Moreover, the complex is humidity sensitive in dry state, and its color changes from bright yellow to bright green when exposed to wet vapor. Unlike other PTCA bisimide derivatives, preparation of the ionic complex of PTCA/β-CDNH2 is simple and avoids complicated synthetic burden. Furthermore, introduction of methanol into the aqueous solution of the complex resulted in aggregation as indicated by solution color change and proved by transmission electron microscopy and dynamic light scattering studies, which explains why the compound in dry state is sensitive to the presence of water and water vapor. X-ray diffraction, UV-vis, and fluorescence studies uncovered the H-packing nature of the structure of the aggregate.

Perylene Derivatives As Useful SERRS Reporters, Including Multiplexing Analysis.

Five perylene bisimide (PBI) derivatives were designed and synthesized, on the basis of quantum-chemical calculations. The influence of halogen substituents on the shape and energy of the frontier orbitals and the Raman spectra were calculated, in the prospect use in surface-enhanced resonance Raman scattering (SERRS) studies. The corresponding experiments confirmed a very strong SERRS response in the presence of pristine (i.e., uncoated) gold nanoparticles. These spectra can be used for multiplexing measurements, namely measurements in which, by using a single laser excitation, one can recognize the simultaneous presence of several analytes.

Theoretical investigations of charge carrier transport in organic semiconductors of naphthalene bisimides N-substituted with alkoxyphenyl groups

Three novel alkoxyphenyl N-substituted naphthalene bisimide derivatives, N,N′-bis(4-n-butoxyphenyl)-1,8:4,5-naphthalenetetracarboxylic (NBI1), N,N′-bis(4-n-hexyloxyphenyl)-1,8:4,5-naphthalenetetracarboxylic (NBI2), and N,N′-bis(4-n-octyloxyphenyl)-1,8:4,5-naphthalenetetracarboxylic (NBI3) as potential organic semiconductors, have been investigated using density functional theory calculations coupled with the incoherent charge-hopping model at the molecular and crystal levels. The calculated results demonstrate that the low-lying and delocalized LUMOs and larger adiabatic electron affinities of these compounds are beneficial to their stability when acting as n-type organic semiconductors. The reorganization energy and transfer integral can significantly influence the charge carrier mobility. The compounds featured with the small reorganization energy and large transfer integral have relatively high charge mobilities. The electron coupling among the dominant hopping pathways indicates that the charge-transport processes happen in the parallel dimer of neighboring molecules with π–π interaction. The investigation of the angle dependence of charge carrier mobility showed that both NBI1 and NBI3 crystals exhibit remarkable anisotropic charge transporting behaviors. The calculated absorption spectra by the time-dependent density functional theory revealed that the strongest absorption peaks in the visible region are assigned to the π → π* transition and these peaks are regulated by the transitions of HOMO → LUMO. The calculated electron mobilities of NBI1, NBI2, and NBI3 are 0.0365, 0.0312, and 0.0801 cm2 V–1 s–1, respectively, indicating that these compounds are suitable for n-type organic semiconductors.

A new perylene bisimide-armed calix[4]-aza-crown as “turn on” fluorescent sensor for Hg2+ ion and its application to living cells

We report the design and synthesis of a new perylene bisimide derivative containing calix[4]arene units (PB-CX[4]) as “turn on” fluorescent sensor for Hg2+ ion determination. PB-CX[4] showed highly selective and sensitive “turn-on” fluorescent responses toward Hg2+ ion based on photoinduced electron transfer (PET) mechanism in DMF/H2O (v/v, 95/5). The binding analysis using a Job plot suggested that PB-CX[4] formed a 1:2 complex with Hg2+. The association constant (K) of PB-CX[4]–Hg2+ complex was found to be 1.66×109M−2, with a detection limit of 5.56×10−7M. In addition, possible utilization of PB-CX[4] as bio-imaging fluorescent probe to detect Hg2+ in human colon cancer cell lines was also observed by confocal fluorescence microscopy.

Molecular size, shape, and electric charges: essential for perylene bisimide-based DNA intercalator to localize in cell nuclei and inhibit cancer cell growth.

The molecular properties concerning size, shape, and electric charges of the planar aromatic DNA intercalators are still poorly understood. Herein, a series of water-soluble perylene bisimide (PBI) derivatives containing a rigid and planar aromatic nanoscaffold with different size, shape, and electric charges were synthesized. Using histochemistry and cell viability assays on animal tissues and cancer cells, we revealed the molecular properties required for successful DNA intercalators to localize in cell nuclei and inhibit cancer cells. Small molecular size and the strong polarity of hydrophilic substituents are prerequisites for PBI-based DNA intercalators. A large number of charges facilitate the nucleic accumulation of these DNA intercalators, while fewer charges and planar aromatic nanoscaffold more efficiently inhibit cancer cell growth.

Regioisomerically Pure 1,7‐Dibromo‐Substituted Perylene Bisimide Dyes: Efficient Synthesis, Separation, and Characterization

Abstract1,7‐Dibromo‐substituted perylene bisimides have been obtained in yields of at least 60 % in regioisomerically pure form by treating the commonly used dibromoperylene‐3,4,9,10‐tetracarboxylic dianhydride with 2‐(diethylamino)ethylamine or 2‐(dimethylamino)ethylamine and then separating the 1,7‐isomer from the regioisomeric mixtures by conventional column chromatography and without recrystallization. The individual regioisomers were fully characterized by 1H NMR spectroscopy and HRMS. The signals of the protons located in the aromatic region and neighboring the imide nitrogen atom were utilized to confirm the chemical structures of the isomers. The 1,7‐dibromo isomer obtained with 2‐(dimethylamino)ethylamine in such a convenient and efficient way was further used to prepare 1,7‐disubstituted perylene bisimide derivatives by saponification, amidation, and then bay‐position substitution reactions. These compounds exhibited a significant redshift and broadening of their absorption and emission in optical spectroscopy analysis.

Self-assembly directed template photopolymerization of perylenebisimide-poly (4-vinylpyridine): Nano organization

A perylene bisimide derivative (PDP-UPBIAcry) having hydroxyl moieties at one termini and polymerizable acrylic units at the other termini was supramolecularly complexed with the pyridine units of Poly (4-vinyl pyridine) (P4VP), followed by photoinduced polymerization of the acrylic units to obtain lamellar organization in the <10 nm range. 1H NMR studies including variable temperature (20 °C−70 °C) measurements were undertaken in DMSO-d6 (anhydrous, extra dry) to understand the interaction between PDP-UPBIAcry and P4VP. The aromatic perylene protons of PDP-UPBIAcry registered an upfield chemical shift while the pyridine protons of P4VP exhibited small downfield shift in their 1:1 supramolecular complex. The hydrogen bonding interaction between pyridyl nitrogen and phenolic OH group was also traced in non-polar media like CDCl3 in model complexes of 4-vinyl pyridine (4VP) with PDP-UPBIAcry. Wide angle X-ray diffraction (WXRD) technique was used to study the bulk structure. Transmission electron microscopy (TEM) imaging revealed highly ordered layered assembly formed upon complexation. Observation from DFT energy minimization studies were correlated with X-ray diffraction data of the supramolecular complex [P4VP (PDP-UPBIAcry)]1.0 to understand the nature of packing of PDP-UPBIAcry that lead to the formation of highly ordered lamellar stacks alternating with P4VP. The higher ordering in the supramolecular polymer complex was also confirmed by the quenching of fluorescence and reduced fluorescence life times of thin solid films of the [P4VP Poly(PDP-UPBIAcry)]1.0 sample.

Dipole-moment-driven cooperative supramolecular polymerization.

While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers.

Synthesis and predetermined supramolecular chirality of carbohydrate-functionalized perylene bisimide derivatives.

Eight carbohydrate-modified perylene bisimides (PBI-4 lac-2 lac, PBI-4 lac-2 Man, PBI-4 lac-2 Gal, PBI-4 lac-2 Mal, PBI-4 Man-2 Man, PBI-4 Man-2 lac, PBI-4 Man-2 Gal and PBI-4 Man-2 Mal) were synthesized, and the following predetermined supramolecular chirality rule was found: perylene bisimides modified with disaccharides (D-lactose and D-maltose) at the imide position generated right-handed chirality, and those modified with monosaccharides (D-mannose and D-galactose) generated left-handed chirality, when D-lactose or D-mannose was substituted in the bay positions of perylene bisimides with amide bonds as the linking spacers. These results may be because of the difference in the stacking angle of the perylene bisimide backbones induced by the steric effect and the additional hydrogen bonds between the disaccharide residues. This study provides an important design rule for predetermined chiral self-assembly of perylene bisimides.