Understanding the Electronic Structure of Larger Azaacenes through DFT Calculations

Although azapentacenes have been widely demonstrated as promising candidates for n-type organic semiconductor devices, the exploration of larger azaacenes is still a challenge. In particular, theoretical studies on the electronic structures of larger azaacenes and the influence of N substitution on the ground states are still rare. Herein, we reported our investigation on the electronic ground-state characters of larger azaacenes through density functional theory (DFT) calculations. Our results indicated that larger azaacenes (fused aromatic rings larger than 6) would show open-shell singlet biradical characters and the introduction of more N atoms into the backbone of large acenes could favor their closed-shell ground states. Interestingly, azahexacenes with three or more N atoms (compounds N64–N68) and azaheptacenes (compound N74) with fourteen N atoms displayed closed-shell singlet ground states compared with the open-shell singlet diradical ground states for larger acenes. Our theoretical studies may guide the design and synthesis of larger azaacenes, which are the promising n-type organic semiconducting materials.     

$$\pi$$-Conjugated Heterocyclic fused Bithiophene Materials

This article covers the developments on the synthesis and properties of heterocyclic fused π-conjugated bithiophene materials that are potentially applicable in molecular electronics and optoelectronics. This fairly young strategy to efficiently tuning the electronic properties generates materials with very narrow band gaps. The nature of the central bridging heteroatom has a significant impact on the electronic and luminescence properties of these materials leading to intriguing species that can be employed in organic light emitting diodes (OLEDs) or organic field effect transistors (OFETs). So far a variety of heteroelements of group 13–16 (B, Si, Ge, Sn, N, P, S) have been investigated and incorporated into molecular as well as polymeric systems. A significant number of these materials can potentially act as organic emitters, electron or hole transport materials in organic devices but further studies are needed to optimize the necessary properties for the utility of this young class of compound in molecular electronics.     

Char structural ordering during pyrolysis and combustion and its influence on char reactivity

In the present study, two processes, thermal treatment and oxidation, were separated for a fundamental study of structural evolution during pyrolysis and combustion, as well as for the study of the influence of such evolution on char reactivity. Chars were prepared at different temperatures and heating rates from a size-graded low volatile bituminous coal. The reactivity of resultant chars was measured in Kinetic Regime I using a fixed bed reactor. The structure of fresh and partly burnt chars was characterized using quantitative XRD analysis (QXRDA), high-resolution TEM (HRTEM), high-resolution FESEM, and multi-point gas adsorption.Both QXRDA and HRTEM observations show that char structure becomes more ordered with increasing pyrolysis temperature and decreasing heating rate. Char structure was also investigated as a function of char burnoff. The QXRDA results show that the amorphous concentration of char decreases during combustion while the aromaticity and average crystallite size of char increase. As a result, char structure becomes more ordered during combustion. This is in agreement with HRTEM observations. Due to the low reaction temperature (about 673 K), which is much lower than that for char preparation (1473 K), it was believed that oxidation, instead of thermal effect, contributed to the structural ordering observed during combustion. The structural parameters obtained from QXRDA were then correlated to char reactivity. Structural ordering was found to be responsible for char deactivation during thermal treatment and oxidation. Since the amorphous concentration and aromaticity of char are two strongest indicators of char reactivity, a structural disorder index, DOI, was defined based on them to describe char structural evolution, and further correlated to char reactivity.     

Correlation of reactivity to hydrogenation and chemical structure of lignites

Three North Dakota lignites with almost the same percentage carbon have been used to determine the relation between chemical structure and reactivity to hydrogenation. Average structural indices of the lignites were estimated using the pyridine-soluble products after alcohol-alkali treatment, the structural indices obtained at various reaction times being extrapolated to zero reaction time. Hydrogenation was influenced by the average structure, with the lignite having higher aromaticity, higher molecular weight of the pyridine extract from the alcohol-alkali reaction product, larger aromatic ring size and lower content of aliphatic structure, showing a smaller degree of conversion.     

Poly(butyl acrylate) polymer enhanced phase segregation and morphology of organic semiconductor for solution-processed thin film transistors

The phase segregation as a result of mixing organic semiconductors with polymeric additives has been reported as an intriguing avenue to optimize semiconductor crystal microstructure, active layer composition and charge carrier transport. In this work, we report the mixing of organic semiconductor 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) with poly(butylacrylate) as a polymer additive to control the semiconductor crystal growth and morphology. The incorporation of poly(butylacrylate) induces a vertical phase segregation but a more predominant lateral phase segregation with TIPS pentacene. Along with a solvent vapor annealing technique, poly(butylacrylate) evenly distributes the semiconductor nuclei on the polymer matrix, and results in organic crystal with enlarged grain width. In addition, the randomized crystal growth of TIPS pentacene has been significantly reduced, giving rise to a 25-fold decrease in misorientation angle. The bottom-gate, top-contact thin film transistors with the poly(butylacrylate)/TIPS pentacene mixture as the active layer demonstrated an improved hole mobility of 0.11 cm²/Vs. We believe the phase segregation induced by the poly(butylacrylate) polymer as well as the solvent vapor annealing method as reported in this work can be facilely replicated on other organic semiconductors to realize high performance organic electronic device applications.     

Structure Modification and Spectroscopic Properties of Artificial Porphyrinoids

In this review article, we summarize our recent progress in rational structure modification and spectroscopic studies of artificial porphyrinoids. Structural modifications, including meso aryl substitution, peripheral aromatic ring fusion, ring contraction and expansion, and core modification with heterocyclic subunits other than pyrrole, perturb the electronic structures and aromaticity of porphyrinoids, thus regulating their electronic properties. The relationship between structure and spectroscopic properties as well as the applications of these porphyrinoids are also reviewed.     

Langevin-schroedinger formulation of electronic tunneling through a molecular bridge with a dissipative acceptor

Modeling electronic tunneling through molecular bridges is desired in order to understand the mechanism of long-range electron transfer reactions in nature, as well as for the design of novel molecular electronics devices. Particularly interesting is the effect of the nuclear motion at the molecular bridge on the electron transfer mechanism and rate. In this work we study the effect of electronic nuclear coupling at the molecular bridge on a unidirectional electronic tunneling process from an electron donor into a dissipative acceptor, as may appear in controlled electron transfer reactions at biological membranes, or in heterogeneous electron transfer reactions. The model includes a collection of harmonic bath modes coupled to the dissipative acceptor site and a single mode at the molecular bridge. The parameters of the dissipative bath are tuned such that the electronic population decays from the donor to the acceptor. This process is simulated using a time-dependent nonlinear Langevin-Schroedinger equation, based on a mean-field approximation for the electronic-nuclear coupling at the acceptor site and a numerically exact treatment of the electronic-nuclear coupling at the molecular bridge. The simulations at zero temperature and weak electronic-nuclear coupling demonstrate that electronic tunneling is promoted by coupling to the nuclear mode at the bridge. This result is consistent with our previous studies of electronic tunneling oscillations in a symmetric donor-bridge-acceptor complex, and it emphasizes the importance of electronic nuclear coupling in analyzing long-range electron transfer processes through molecular bridges or wires.     

Biomaterials‐based organic electronic devices

Organic electronic devices have demonstrated tremendous versatility in a wide range of applications including consumer electronics, photovoltaics and biotechnology. The traditional interface of organic electronics with biology, biotechnology and medicine occurs in the general field of sensing biological phenomena. For example, the fabrication of hybrid electronic structures using both organic semiconductors and bioactive molecules has led to enhancements in the sensitivity and specificity within biosensing platforms, which in turn has a potentially wide range of clinical applications. However, the interface of biomolecules and organic semiconductors has also recently explored the potential use of natural and synthetic biomaterials as structural components of electronic devices. The fabrication of electronically active systems using biomaterials‐based components has the potential to produce a large set of unique devices including environmentally biodegradable systems and bioresorbable temporary medical devices. This article reviews recent advances in the implementation of biomaterials as structural components in organic electronic devices with a focus on potential applications in biotechnology and medicine. Copyright © 2010 Society of Chemical Industry     

Special Sites at Noble and Late Transition Metal Catalysts

An overview of recent advancements in density functional theory modeling of particularly reactive sites at noble and late transition metal surfaces is given. Such special sites include sites at the flat surfaces of thin metal films, sites at stepped surfaces, sites at the metal/oxide interface boundary for oxide-supported metal clusters, and sites at the perimeter of oxide islands grown on metal surfaces. The Newns–Anderson model of the electronic interaction underlying chemisorption is described. This provides the grounds for introducing the Hammer–N?rskov d-band model that correlates changes in the energy center of the valence d-band density of states at the surface sites with their ability to form chemisorption bonds. A reactivity change described by this model is characterized as an electronic structure effect. Br?nsted plots of energy barriers versus reaction energies are discussed from the surface reaction perspective and are used to analyze the trends in the calculated changes. Deviations in the relation between energy barriers and reaction energies in Br?nsted plots are identified as due to atomic structure effects. The reactivity change from pure Pd surfaces to Pd thin films supported on MgO can be assigned to an electronic effect. Likewise for the reactivity change from flat Au surfaces, over Au thin films to Au edges and the Au/MgO interface boundary. The reactivity enhancement at atomic step sites is of both electronic and atomic structure nature for NO dissociation at Ru, Rh and Pd surfaces. The enhancement of the CO oxidation reactivity when moving from a CO+O coadsorption structure on Pt(111) to the PtO₂ oxide island edges supported by Pt(111) is, however, identified as mainly an atomic structure effect. As such, it is linked to the occurrence of favorable pathways at the oxide island edges and is occurring despite of stronger adsorbate binding of the oxygen within the oxide edge, i.e. despite of an opposing electronic effect. As a final topic, a discussion is given of the accuracy of density functional theory in conjunction with surface reactions; adsorption, desorption, diffusion, and dissociation. Energy barriers are concluded to be more robust with respect to changes in the exchange-correlation functional than are molecular bond and adsorption energies.     

From coal to single-stage and two-stage products: A reactive model of coal structure

Using detailed chemical analyses of both coal and products from various liquefaction schemes, molecular models have been constructed to show the steps in the conversion process, and the nature of the products. Products from short- and long-contact time dissolution are shown in relation to structures found in the parent coal. Such molecules are highly functional, high molecular weight materials, which are difficult to process by conventional methods and tend to associate causing product stability problems. In contrast, products from two-stage liquefaction have greatly reduced molecular weight and functionality, and are consequently more amenable to downstream processing. The accurate and quantitative presentation of models reflects the analytical data on the coal and liquefaction products in terms of elemental distribution, aromaticity, functional group chemistry, and reactivity.     

Nanographenes as active components of single-molecule electronics and how a scanning tunneling microscope puts them to work

Single-molecule electronics, that is, realizing novel electronic functionalities from single (or very few) molecules, holds promise for application in various technologies, including signal processing and sensing. Nanographenes, which are extended polycyclic aromatic hydrocarbons (PAHs), are highly attractive subjects for studies of single-molecule electronics because the electronic properties of their flat conjugated systems can be varied dramatically through synthetic modification of their sizes and topologies. Single nanographenes provide high tunneling currents when adsorbed flat onto conducting substrates, such as graphite. Because of their chemical inertness, nanographenes interact only weakly with these substrates, thereby preventing the need for special epitaxial structure matching. Instead, self-assembly at the interface between a conducting solid, such as the basal plane of graphite, and a nanographene solution generally leads to highly ordered monolayers. Scanning tunneling spectroscopy (STS) allows the current-voltage characteristics to be measured through a single molecule positioned between two electrodes; the key to the success of STS is the ability to position the scanning tunneling microscopy (STM) tip freely with respect to the molecule in all dimensions, that is, both parallel and perpendicular to the surface. In this Account, we report the properties of nanographenes having sizes ranging from 0.7 to 3.1 nm and exhibiting various symmetry, periphery, and substitution types. The size of the aromatic system and the nature of its perimeter are two essential features affecting its HOMO-LUMO gap and charge carrier mobility in the condensed phase. Moreover, the extended pi area of larger substituted PAHs improves the degree of self-ordering, another key requirement for high-performance electronic devices. Self-assembly at the interface between an organic solution and the basal plane of graphite allows deposition of single molecules within the well-defined environment of a molecular monolayer. We have used STM and STS to investigate both the structures and electronic properties of these single molecules in situ. Indeed, we have observed key electronic functions, rectification and current control through single molecules, within a prototypical chemical field-effect transistor at ambient temperature. The combination of nanographenes and STM/STS, with the PAHs self-assembled in oriented molecular mono- or bilayers at the interface between an organic solution and the basal plane of graphite and contacted by the STM tip, is a simple, reliable, and versatile system for developing the fundamental concepts of molecular electronics. Our future targets include fast reversible molecular switches and complex molecular electronic devices coupled together from several single-molecule systems.     

Experimental and theoretical approaches to the study of TMI-zeolite (TM = Fe, Co, Cu)

Transition metal ions in zeolites TMI-zeolite (TM = Fe, Co, Cu) attract great attention due to their potentialities as catalysts. In the recent years, the high efficiency of TMI-zeolites for the selective catalytic reduction (SCR) of contaminated flue gases has been demonstrated. It has been shown that the structure of the framework, the nature and location of extraframework cation species play a fundamental role in the process. Experimental results based on spectroscopies, as well as on reactivity studies have led to valuable insights about the structure of cationic sites as well as about the active species involved during the catalytic reactions. However, it is not sufficient to obtain all this information. This review reporting density functional theory (DFT) calculations shows that a molecular approach is very useful and has become an indispensable tool for the determination of the geometries, the electronic structures, the spectroscopic properties and the reactivity of TMI-zeolites.     

The evolution of graphene-based electronic devices

Successful isolation of single-layer graphene, the two-dimensional allotrope of carbon from graphite, has fuelled a lot of interest in exploring the feasibility of using it for fabrication of various electronic devices, particularly because of its exceptional electronic properties. Graphene is poised to save Moore's law by acting as a successor of silicon-based electronics. This article reviews the success story of this allotrope with a focus on the structure, properties and preparation of graphene as well as its various device applications.     

Scanning tunneling spectroscopy of molecules on insulating films

Ultrathin insulating films on metal substrates are unique systems for using a scanning tunneling microscope (STM) to study the electron transport properties in the weak-coupling limit. The electronic decoupling provided by the films allows the direct imaging of the unperturbed molecular orbitals, as will be demonstrated in the case of individual pentacene molecules. The coupling between electronic states localized on the adsorbate and optical phonons in a polar insulator has two important implications: Peaks in conductance spectra resulting from resonant tunneling into electronic states of the molecules are significantly broadened by the presence of the insulator. Second, the ionic relaxations in a polar insulator may lead to an interesting charge bistability in atoms and molecules. STM-based molecular manipulation has been used to form a metallo-organic complex as well as to switch the position of the two hydrogen atoms in the inner cavity of single free-base naphthalocyanine molecules.     

Towards type-selective carbon nanotube growth at low substrate temperature via photo-thermal chemical vapour deposition

Carbon nanotubes have been intensively researched for electronic applications, driven by their excellent electronic properties, where the goals are control and reproducibility of growth, semiconducting/metallic type selectivity and maintaining high quality of carbon nanotubes, in a process that is temperature-compatible with the electronics. Photo-thermal chemical vapour deposition can achieve these goals and, through a thorough investigation of the parameter space, we achieve very high nanotube-quality and growth rates, and produce a phase-diagram that reveals distinct regions for growing semiconducting and metallic single-walled nanotubes, as well as multi-walled. Correlation with the carbon-catalyst phase diagram allows for the development of a novel growth model. We propose that the temperature-gradient induces carbon diffusivity-gradient across the catalyst to yield the high growth rate. This is attributed to the increase of α-iron of catalyst. The growth control demonstrated here allows for integration of the nanotube growth process by photo-thermal deposition into mainstream electronics manufacture.     

From nanofabrication to self-fabrication--tailored chemistry for control of single molecule electronic devices

Single molecule electronics is a field of research focused on the use of single molecules as electronics components. During the past 15 years the field has concentrated on development of test beds for measurements on single molecules. Bottom-up approaches to single molecule devices are emerging as alternatives to the dominant top-down nanofabrication techniques. One example is solution-based self-assembly of a molecule enclosed by two gold nanorod electrodes. This article will discuss recent attempts to control the self-assembly process by the use of supramolecular chemistry and how to tailor the electronic properties of a single molecule by chemical design.     

The electronic properties of superatom states of hollow molecules

Electronic and optical properties of molecules and molecular solids are traditionally considered from the perspective of the frontier orbitals and their intermolecular interactions. How molecules condense into crystalline solids, however, is mainly attributed to the long-range polarization interaction. In this Account, we show that long-range polarization also introduces a distinctive set of diffuse molecular electronic states, which in quantum structures or solids can combine into nearly-free-electron (NFE) bands. These NFE properties, which are usually associated with good metals, are vividly evident in sp(2) hybridized carbon materials, specifically graphene and its derivatives. The polarization interaction is primarily manifested in the screening of an external charge at a solid/vacuum interface. It is responsible for the universal image potential and the associated unoccupied image potential (IP) states, which are observed even at the He liquid/vacuum interface. The molecular electronic properties that we describe are derived from the IP states of graphene, which float above and below the molecular plane and undergo free motion parallel to it. Rolling or wrapping a graphene sheet into a nanotube or a fullerene transforms the IP states into diffuse atom-like orbitals that are bound primarily to hollow molecular cores, rather than the component atoms. Therefore, we named them the superatom molecular orbitals (SAMOs). Like the excitonic states of semiconductor nanostructures or the plasmonic resonances of metallic nanoparticles, SAMOs of fullerene molecules, separated by their van der Waals distance, can combine to form diatomic molecule-like orbitals of C(60) dimers. For larger aggregates, they form NFE bands of superatomic quantum structures and solids. The overlap of the diffuse SAMO wavefunctions in van der Waals solids provides a different paradigm for band formation than the valence or conduction bands formed by interaction of the more tightly bound, directional highest occupied molecular orbitals (HOMOs) or the lowest unoccupied molecular orbitals (LUMOs). Therefore, SAMO wavefunctions provide insights into the design of molecular materials with potentially superior properties for electronics. Physicists and chemists have thought of fullerenes as atom-like building blocks of electronic materials, and superatom properties have been attributed to other elemental gas-phase clusters based on their size-dependent electronic structure and reactivity. Only in the case of fullerenes, however, do the superatom properties survive as delocalized electronic bands even in the condensed phase. We emphasize, however, that the superatom states and their bands are usually unoccupied and therefore do not contribute to intermolecular bonding. Instead, their significance lies in the electronic properties they confer when electrons are introduced, such as when they are excited optically or probed by the atomically sharp tip of a scanning tunneling microscope. We describe the IP states of graphene as the primary manifestation of the universal polarization response of a molecular sheet and how these states in turn define the NFE properties of materials derived from graphene, such as graphite, fullerenes, and nanotubes. Through low-temperature scanning tunneling microscopy (LT-STM), time-resolved two-photon photoemission spectroscopy (TR-2PP), and density functional theory (DFT), we describe the real and reciprocal space electronic properties of SAMOs for single C(60) molecules and their self-assembled 1D and 2D quantum structures on single-crystal metal surfaces.     

Graphene‐based electrodes for flexible electronics

As ‘flexibility’ has emerged as an important issue in next‐generation electronics, many efforts to find new classes of materials have been devoted to realizing stretchable, bendable and foldable electronic devices. For these devices to be realized, graphene has been considered as one of the most promising candidates for flexible electrodes due to its extraordinary electrical, optical and mechanical properties. Particularly, recent developments in the fabrication and modification of graphene point to a bright future for graphene electrodes in flexible electronics. This mini‐review summarizes the recent progress in graphene films as flexible electrodes for various applications such as solar cells, organic light‐emitting diodes, touchscreens, transistors and supercapacitors. © 2015 Society of Chemical Industry     

Dynamic processes leading to covalent bond formation for S(N)1 reactions

The SN1 reaction mechanism is one of the most fundamental processes in organic chemistry. As such, it has been the subject of study for over 70 years with the purpose of seeking to understand the fundamental parameters that control reactivity. With recent advances in both electronic structure theory and condense-phase reaction dynamics theory as well as in experimental probes of these reactions on the femtosecond and picosecond time scale, we are beginning to gain new insights into the nature of these reactions.