Naphthalene Bis Research Articles

π-Extended benzo[1,2:4,5]di[7]annulene bis(dicarboximide)s - a new class of non-alternant polycyclic aromatic dicarboximides.

Aromatic dicarboximides are a class of molecules represented by the well-known rylene bis(dicarboximide)s, in particular perylene or naphthalene bis(dicarboximide)s, which show pronounced optoelectronic properties and are applied as color pigments, fluorescent dyes and organic semiconductors. Herein we extend the family of aromatic bis(dicarboximide)s and report the synthesis of the first series of non-alternant aromatic dicarboximides by twofold Pd-catalyzed [5 + 2] annulation. Characterization by UV/vis spectroscopy and cyclic voltammetry (CV) measurements give insight into the optoelectronic characteristics of the hitherto unexplored substance class of heptagon-containing imides. Theoretical studies by nucleus independent chemical shift (NICS) XY-scans and anisotropy of the induced current density (ACID) plots demonstrate the influence of both the non-alternant carbon framework and the imide moieties on aromaticity of the synthesized bisimides.

Optoelectronic properties of naphthalene bis-benzimidazole based derivatives and their photovoltaic applications

In the current study, the four molecules (F1-F4) have been designed to augment the efficiency of organic photovoltaic (OPV) devices by employing different acceptor moieties named as 2-methylenemalononitrile (F1), 2-(2-methylene-3-oxo-2,3-dihydroinden-1-ylidene) malononitrile (F2), 3-methyl-5-methylene-2-thioxothiazolodin-4-one (F3) and methyl 2-cyanoacrylate (F4). All the designed molecules shared same acceptor core named as naphthalene bis benzimidazole linked with acceptor groups at peripheral positions through thiophene. Comparative analysis has been conducted using selected hybrid functional WB97XD/6-31G (d, p) between designed molecules and reference molecule to interpret their optoelectronic properties such as Frontier molecular orbitals, Density of States, Reorganization energies, Transition density matrix analysis. Optical properties at TD-DFT predicted that F2 molecule has better UV-absorption as compared to reference molecule R. Reorganization energies, lower binding energies and higher open circuit voltage values have been predicted which showed that these designed molecules could be the best substitute for charge transporting materials. All these theoretical calculations showed that the designed acceptor molecules have outstanding optoelectronic properties in future utilization as compared with reference molecule.

Processable High Electron Mobility π‐Copolymers via Mesoscale Backbone Conformational Ordering

AbstractThe synthesis and experimental/theoretical characterization of a new series of electron‐transporting copolymers based on the naphthalene bis(4,8‐diamino‐1,5‐dicarboxyl)amide (NBA) building block are reported. Comonomers are designed to test the emergent effects of manipulating backbone torsional characteristics, and density functional theory (DFT) analysis reveals the key role of backbone conformation in optimizing electronic delocalization and transport. The NBA copolymer conformational and electronic properties are characterized using a broad array of molecular/macromolecular, thermal, optical, electrochemical, and charge transport techniques. All NBA copolymers exhibit strongly aggregated morphologies with significant nanoscale order. Copolymer charge transport properties are investigated in thin‐film transistors and exhibit excellent electron mobilities ranging from 0.4 to 4.5 cm2 V−1 s−1. Importantly, the electron transport efficiency correlates with the film mesoscale order, which emerges from comonomer‐dependent backbone planarity and extension. These results illuminate the key NBA building block structure–morphology–bulk property design relationships essential for processable, electronics‐applicable high‐performance polymeric semiconductors.

Angular-Shaped Naphthalene Bis(1,5-diamide-2,6-diylidene)malononitrile for High-Performance, Air-Stable N-Type Organic Field-Effect Transistors.

The synthesis, characterization, and application of two angular-shaped naphthalene bis(1,5-diamide-2,6-diylidene)malononitriles (NBAMs) as high-performance air-stable n-type organic field effect transistor (OFET) materials are reported. NBAM derivatives exhibit deep lowest-unoccupied molecular orbital (LUMO) levels, suitable for air-stable n-type OFETs. The OFET device based on NBAM-EH fabricated by vapor deposition exhibits a maximum electron mobility of 0.63 cm2 V-1 s-1 in air with an on/off current ratio ( Ion/ Ioff) of 105.

Naphthalene Bis(4,8-diamino-1,5-dicarboxyl)amide Building Block for Semiconducting Polymers.

We report a new naphthalene bis(4,8-diamino-1,5-dicarboxyl)amide (NBA) building block for polymeric semiconductors. Computational modeling suggests that regio-connectivity at the 2,6- or 3,7-NBA positions strongly modulates polymer backbone torsion and, therefore, intramolecular π-conjugation and aggregation. Optical, electrochemical, and X-ray diffraction characterization of 3,7- and 2,6-dithienyl-substituted NBA molecules and corresponding isomeric NBA-bithiophene copolymers P1 and P2, respectively, reveals the key role of regio-connectivity. Charge transport measurements demonstrate that while the twisted 3,7-NDA-based P1 is a poor semiconductor, the planar 2,6-functionalized NBA polymers (P2-P4) exhibit ambipolarity, with μe and μh of up to 0.39 and 0.32 cm2/(V·s), respectively.

Epitaxially-crystallized oriented naphthalene bis(dicarboximide) morphology for significant performance improvement of electron-transporting thin-film transistors.

Large-area highly-ordered F-NDI films were obtained by epitaxial-crystallization on highly-oriented PE substrates through vacuum deposition. An electron mobility of 0.2 cm(2) V(-1) s(-1) was achieved based on such epitaxially-crystallized F-NDI films, which is 4 times higher than that of its un-oriented thin film devices.

High performance n-type single crystalline transistors of naphthalene bis(dicarboximide) and their anisotropic transport in crystals

High-performance n-type organic single crystal transistors of a naphthalene diimide are demonstrated. The accomplished transistors exhibit electron mobility as high as 0.7 cm(2) V(-1) s(-1). The anisotropic charge transport in the elongated hexagonal crystals of the naphthalene diimide is also explored. The transport anisotropy along different directions is at least 1.6 (mobility ratio).

N-Channel Organic Thin-Film Transistors based on Naphthalene–Bis(dicarboximide) Polymer for Organic Transistor Memory Using Hole-Acceptor Layer

An investigation of threshold voltage shifts in organic thin-film transistors (OTFTs) based on poly[N,N '-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) [P(NDI2OD-T2)] with additional poly(3-hexylthiophene) (P3HT) films on a poly(methyl methacrylate) (PMMA) organic dielectric layer is reported. With a top source-drain contact structure, the device exhibited a unipolar property with n-channel characteristics similar to those of the P(NDI2OD-T2)-only device. Furthermore, the existence of P3HT films as hole acceptor-like storage layers resulted in reversible Vth shift upon the application of external gate bias (Vbias) for a certain bias time (Tbias). Hence, the P(NDI2OD-T2)/P3HT-OTFTs exhibited a large memory window (ΔVth = 10.7 V) for write and erase electrically without major degradation in saturation mobility [µsat = (1.8–2.8) ×10-4 cm2 V-1 s-1]. These results clearly indicate the utility of the naphthalene–bis(dicarboximide) (NDI)-based polymer–hole acceptor layer in the development of n-channel organic transistor memories.

N-Channel Organic Thin-Film Transistors based on Naphthalene–Bis(dicarboximide) Polymer for Organic Transistor Memory Using Hole-Acceptor Layer

n-Channel Organic Thin-Film Transistors based on Naphthalene–Bis(dicarboximide) Polymer for Organic Transistor Memory Using Hole-Acceptor Layer

Physical Properties, Charge Carrier Mobility, and Photovoltaic Performance of Dendritic Oligothiophene Bearing Naphthalene Bis(dicarboximide) Groups

Dendritic oligothiophene having naphthalene bis(dicarboximide) (NDI) was synthesized, and its physical properties were investigated by ultraviolet–visible (UV–vis) spectroscopy and cyclic voltammetry. The charge carrier mobility measurements by organic field-effect transistor devices and flash-photolysis time-resolved microwave conductivity measurements revealed p-channel behavior. The photovoltaic performance of the dendritic oligothiophene–NDI dyad with PCBM exhibited a power conversion efficiency of 0.14%.

Light Intensity Effects on Photoinduced Charge Separation Parameters in a Molecular Triad Based on an Iridium(III) Bis(terpyridine) Unit

The effect of photon flux on the yield and lifetime of charge separation over the extreme components of a D-Ir-A triad, where D is a triphenyl amine electron donor, A is a naphthalene bis(imide) electron acceptor and Ir is an Ir(III) bis(terpyridine) complex, has been investigated. In usual laboratory conditions, with nanosecond and picosecond laser pulses in the 4-8 mJ range, biphotonic processes take place. Biphotonic products and their evolution can introduce complications in reaction mechanisms and their interpretation but can also drastically reduce the yield and the lifetime of the charge-separated state. In the present case, after discussion of several possible mechanisms, the process detrimental to charge separation is ascribed to absorption of a photon by the photogenerated charge-separated state D(+)-Ir-A(-).

Metal bisphosphonate multilayers of perylene and naphthalene bis(dicarboximide) derivatives on ITO substrate

Two phosphonate-terminated redox molecules, which are N, N′-bis(ethyl dihydrogen phosphate)-3,4,9,10-perylene bis(dicarboximide) (EPPI) and N, N′-bis(ethyl dihydrogen phosphate)-1,4,5,8-naphthalene(dicarboximide) (EPNI), are adsorbed on indium-tin-oxide (ITO) substrate pretreated with ZrOCl 2. Multilayer films of Zr-EPPI and Zr-EPNI were grown layer-by-layer on the substrate by the subsequent treatment of alternate dipping into aqueous ZrOCl 2 and EPPI or EPNI solution. The layer growth and electron transfer from ITO to the multilayer were investigated with UV–VIS absorption and cyclic voltammetry.

Highly Sensitive Probe for Gene Analysis by Electrochemical Approach

Abstract Electrochemically active DNA ligands, including ferrocenyl DNA oligonucleotides and ferrocenyl naphthalene bis(carboximide), are reviewed in connection with development of an electrochemical DNA sensor. Ferrocenyl oligonucleotides are used as an electrochemical probe DNA detectable by high performance liquid chromatography with the electrochemical detector (HPLC-ECD) system and they enable the target DNA analysis at femto mole level. Ferrocenyl oligonucelotides are useful also as a polymerase chain reaction (PCR) primer to realize quantitative PCR. Ferrocenyl naphthalene bis(carboximide) is a general DNA detecting ligand. When coupled with a probe DNA immobilized on an electrode, the target DNA from plasmid, chromosomal DNA, and total RNA extracted from several sources can be analyzed with very high sensitivity. Ferrocenyl naphthalene bis(carboximide) bound to the DNA duplex serves as a pseudo-polyferrocene array and this unique architecture leads to enhanced electron transfer between reduced glucose oxidase and the electrode. Unpaired base(s) present on the mismatched base(s) of the DNA duplex can be detected by observation of a decrease in the amount of ferrocenyl naphthalene bis(carboximide) bound to such a mismatched DNA duplex. Hybridized DNA on the DNA microarray was visualized electrochemically in the aqueous solution by the scanning electrochemical microscope (SECM) coupled with the ferrocenyl naphthalene bis(carboximide).

Threading Intercalators as a New DNA Structural Probe

Abstract Nogalamycin is a threading intercalator and when it binds with double stranded DNA, one of the two sugar substituents goes between adjacent base pairs of DNA to form a stable complex in which the two substituents of nogalamycin are projecting out in each groove of DNA. Since the molecular volume of the substituents of nogalamycin is larger than that of the space created through the motion of DNA strands constituting the double helix, a cleavage of hydrogen bonds in the base pairs of DNA duplex is necessary to form such a complex. The structure of double-stranded DNA is dynamic, and the base pair cleavage (base pair opening) and re-formation (closing) occur frequently at ambient temperature. A wider variety of threading intercalators is obtainable synthetically, and they include several families such as 1,5-disubstituted anthraquinones, 9,10-disubstituted anthracenes, and naphthalene bis(dicarboximide) derivatives. Kinetic study of the complex formation and dissociation of naphthalene bis(dicarboximide) carrying substituents of different size have made one recognize the dynamic character of duplex DNA in intercalation reaction. A cyclic bis-intercalator was also able to form a threading complex of a catenane-like structure. A thorough study of the binding behavior of natural and synthetic threading intercalators with DNA revealed that a proper design of substituents on threading intercalators can produce ligands which specifically bind either to single- or double-stranded DNA. These ligands, synthetic ones in particular, will hopefully serve not only as new DNA structural probes but also as chemotherapeutic agents.

Self-stacking of naphthalene bis(dicarboximide)s probed by NMR †

The self-stacking in water of a series of naphthalene-1,8∶4,5-bis(dicarboximide)s (also known as naphthalene diimides, NDIs) bearing cationic side chains has been studied using NMR techniques. The position of the charge in the side chain has a strong effect on the propensity of the NDI to self-stack. Examples with a cationic center three atoms away from the NDI ring in general do not self-stack; those with cationic centers further out on the side chains are prone to self-stack at NMR concentrations. The size of the side chain per se does not appear to be a significant controlling factor; even a derivative with biotin side chains shows no evidence of self-stacking. Increasing the ionic strength of the solution can also induce stacking. Derivatives with aromatic side chains can show intramolecular self-stacking of the side chain with the central NDI ring. This is significant for side chains with isoquinoline and bipyridine groups but not significant for side chains with pyridine groups. An example of an NDI that undergoes both intramolecular and intermolecular stacking is the derivative bearing side chains ending in Ru(bpy)32+ moieties. In methanol, the shift patterns of the aromatic resonances of the bipyridine rings are very close to those of a model compound. However, a more complicated chemical shift pattern is seen in water. This indicates that conformations with the Ru(bpy)32+ moieties lying at least partly within the shielding cone of the aromatic NDI system are favored. Molecular modeling indicates that conformations in which the bipyridine ring interacts with the NDI ring are readily achievable. The temperature dependence of the chemical shifts for this molecule indicates that both intramolecular interactions of the bipyridine rings with the NDI ring and self-stacking of the NDI rings are significant.