HOMO–LUMO energy gap control in platinum(ii) biphenyl complexes containing 2,2′-bipyridine ligands

A series of platinum(II) biphenyl 2,2’-bipyridine complexes containing electron-donating and electron-withdrawing moieties on the 4 and 4’ positions of the bipyridine ligand exhibit emission from excited states in the 600 nm region of the spectrum upon excitation in the metal-to-ligand charge transfer transition located near 450 nm. These complexes are distorted from planarity based on both single crystal structure determinations and density functional theory (DFT) calculations of isolated molecules in acetonitrile. The DFT also reveals the geometry of the lowest-lying triplet state (LLTS) of each complex that is important for emission behavior. The LLTS are assigned based on the electron spin density distributions and correlated with the singlet excited states to understand the mechanism of electronic excitation and relaxation. Timedependent DFT calculations are performed to compute the singlet excited state energies of these complexes so as to help interpret their UV-Vis absorption spectra. Computational and experimental results, including absorption and emission energy maxima, electrochemical reduction potentials, LLTS, singlet excited states, and LUMO and HOMO energies, exhibit linear correlations with the Hammett constants for para-substituents σp. These correlations are employed to screen complexes that have not yet been synthesized. The correlation analysis indicates that electronic structure and the HOMO-LUMO energy gap in Pt(II) complexes can be effectively controlled using electron-donating and electron-withdrawing moieties covalently bonded to the ligands. The information presented in this paper provides analysis and better understanding of the fundamental electronic and thermodynamic behavior of these complexes and could be used to design systems with specific applications

Electronic Characteristics and Charge Transport Mechanisms for Large Area Aromatic Molecular Junctions

This paper reports the electron transport characteristics of carbon/molecule/Cu molecular junctions, where aromatic molecules (azobenzene or AB and nitroazobenzene or NAB) are employed as the molecular component. It is shown that these devices can be made with high yield (>90%), display excellent reproducibility, and can withstand at least 1.5 × 10 9 potential cycles and temperatures of at least 180°C. Transport mechanisms are investigated by analysis of current density/voltage (J-V) curves as a function of the molecular layer thickness and temperature. Results show that J decreases exponentially with thickness, giving a measured value for the low-bias attenuation factor ( ) of 2.5 ( 0.1 nm -1 for AB and NAB. In addition, it is shown that transport is not thermally activated over a wide range of temperatures (5-450 K) and that the appearance of a thermally "activated" region at higher temperatures can be accounted for by the effect of temperature on the distribution of electrons around the Fermi level of the contact(s). These results indicate that quantum mechanical tunneling is likely the mechanism for charge transport in these junctions. Although application of the Simmons tunneling model leads to transport parameters consistent with nonresonant tunneling, the parameters obtained from fitting experimental data indicate that the barrier height and/or shape, effective mass, and dielectric constant (ε) can all change with thickness. Experimental measurements of ε and density functional theory (DFT) calculations of molecular energy levels and polarizability support these conclusions. Finally, the implications of the transport mechanisms are discussed from the viewpoint of designing functional molecular electronic devices

UV Stimulated Manganese Dioxide for the Persulfate Catalytic Degradation of Bisphenol A

One of the most commonly produced industrial chemicals worldwide, bisphenol A (BPA), is used as a precursor in plastics, resins, paints, and many other materials. It has been proved that BPA can cause long-term adverse effects on ecosystems and human health due to its toxicity as an endocrine disruptor. In this study, we developed an integrated MnO2/UV/persulfate (PS) process for use in BPA photocatalytic degradation from water and examined the reaction mechanisms, degradation pathways, and toxicity reduction. Comparative tests using MnO2, PS, UV, UV/MnO2, MnO2/PS, and UV/PS processes were conducted under the same conditions to investigate the mechanism of BPA catalytic degradation by the proposed MnO2/UV/PS process. The best performance was observed in the MnO2/UV/PS process in which BPA was completely removed in 30 min with a reduction rate of over 90% for total organic carbon after 2 h. This process also showed a stable removal efficiency with a large variation of pH levels (3.6 to 10.0). Kinetic analysis suggested that 1O2 and SO4

DFT, molecular docking, and ADME/Tox screening investigations of market‑available drugs against SARS‑CoV‑2

A series of drugs was investigated to determine structural, electronic and pharmacological properties, as well as the molecular affinity for the main protease of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). The drugs were submitted to density functional theory calculations to optimize structures and predict binding preferences. The optimized geometries were used in molecular docking simulations. In the docking study, the receiver was considered rigid and the drugs flexible. The Lamarckian genetic algorithm with global search and Pseudo-Solis and Wets with local search were adopted for docking. Absorption, distribution, metabolism, excretion and toxicological properties were obtained from the Pre-ADMET online server. In this series, the antiviral atazanavir showed the potential to inhibit the main protease of SARS-CoV-2, based on the free binding energy, inhibition constant, binding interactions and its favorable pharmacological properties. Therefore, we recommend carrying out further studies with in vitro tests and subsequent clinical tests to analyze its effectiveness in the treatment of SARS-CoV-2

Modeling of bitumen fragment adsorption on Cu+ and Ag+ exchanged zeolite nanoparticles

We investigate bitumen desulfurisation on zeolite chabazite nanoparticles that contain Ag+ and Cu+ by using periodic density functional theory. The large bitumen molecules that contain thiophene derivative impurities and useful aromatic hydrocarbons cannot enter into zeolite pores but adsorb on the outer surface of the zeolite. The zeolite nanoparticle surface can be optimised for efficient impurities removal and bitumen upgrading, as we have shown recently. On chabazite nanoparticle surface, Ag+ that reside near the main channel enhance the bitumen fragment adsorption in the order benzene < thiophene < benzothiophene < dibenzothiophene. For Cu+, the bitumen fragment adsorption strength increases in the order benzene < dibenzothiophene < benzothiophene < thiophene. The different trends arise from the spatial constraint of the surface termination and the smaller ionic radius of Cu+ relative to Ag+. Our results show that zeolite surface modifications allow for stronger adsorption of thiophenes relative to hydrocarbons. Our results can be applied toward the rational design of zeolite nanoparticles for bitumen upgrading. We conclude that the preferred configurations of organic macromolecules adsorbed on zeolite outer surfaces can be safely predicted by using Fukui functions.Peer reviewed: YesNRC publication: Ye

Koopmans' multiconfigurational self-consistent field (MCSCF) Fukui functions and MCSCF perturbation theory

Prediction of chemical reactivity has become one of the highest priority tasks of computational chemistry since the development of the methods of modeling electronic structure. Despite the general simplicity of the physical concept of reactivity and the rapid development of modern density functional theory (DFT) methods, this task remains state-of-the-art for systems with wavefunctions that have a multiconfigurational character. In such cases, for the accurate description of reactivity one needs to use multiconfigurational approaches that are much heavier computationally then ordinary single-determinant DFT methods. Moreover, the complexity of the calculation of reactivity is increased by the necessity to calculate ionic and transition states. These computational challenges can be addressed by employing the concepts of Koopmans' theorem and its extension to a multiconfigurational case. We present a simplified methodology for the calculation of Fukui functions, based on Koopmans' approximation for multiconfigurational Green's functions developed in our previous works. Also, an extension of this methodology based on perturbation theory has been developed to improve accuracy. \ua9 2013 Published by NRC Research Press.Peer reviewed: YesNRC publication: Ye

Density functional theory study of the effects of substituents on the carbon-13 nuclear magnetic resonance chemical shifts of asphaltene model compounds

Petroleum asphaltenes are a complex mixture of organic molecules containing mainly fused polyaromatic and naphthenic systems and pendant chains, polar moieties with heteroatoms (S, N, and O), and transition metals. A variety of spectroscopic techniques has been employed to characterize asphaltenes, but their structures remain largely elusive because of the complexity, variety of samples, and assignment limitations. Carbon-13 nuclear magnetic resonance (13C NMR) spectroscopy has contributed extensively to asphaltene characterization. However, proper assignment of 13C NMR spectra is very challenging because spectra of natural asphaltenes feature a large number of peaks in unusual environments, which may be hard to assign and interpret. We employ the dispersion-corrected \u3c9B97X-D density functional with 6-31G(d,p) basis set to rationalize common trends in the 13C NMR chemical shifts of asphaltene model compounds. The calculated 13C NMR chemical shifts for a calibration series of 14 aromatic and heterocyclic reference compounds containing C atoms of types similar to those in the asphaltene model compounds are found to correlate linearly with the respective experimental values. The linear fitting yields a correlation coefficient of R2 = 0.99 and absolute errors of less than 10 ppm. Moreover, we calculate and calibrate the 13C chemical shifts of asphaltenes extracted from Brazilian vacuum residues to analyze and correlate the C atom types with those of the reference compounds. It is found that the presence of heteroatoms as well as environments with a high aromatic condensation index can significantly affect the chemical shifts. The effect of heteroatoms on the chemical shift, a situation that has scarcely been addressed in the literature, is evaluated here in detail. The results are intended to help interpret 13C NMR spectra and allow for a more complete characterization of asphaltene molecules.Peer reviewed: YesNRC publication: Ye