Effective bimetallic composite catalysts for the synthesis of arylated furans and thiophenes in aqueous media

Chemistry of Heterocyclic Compounds - N-(4,6-Dimethylpyrimidin-2-yl)-5-phenylisoxazole-3-carboxamide was used as a ligand for obtaining bimetallic boron-containing heterogeneous catalysts...     

Binuclear copper(II) complex with 2-imidazolylbenzothiazole and bridged chloride ligands

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Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

On the Motion of Substance in a Channel of a Network: Extended Model and New Classes of Probability Distributions

We discuss the motion of substance in a channel containing nodes of a network. Each node of the channel can exchange substance with: (i) neighboring nodes of the channel, (ii) network nodes which do not belong to the channel, and (iii) environment of the network. The new point in this study is that we assume possibility for exchange of substance among flows of substance between nodes of the channel and: (i) nodes that belong to the network but do not belong to the channel and (ii) environment of the network. This leads to an extension of the model of motion of substance and the extended model contains previous models as particular cases. We use a discrete-time model of motion of substance and consider a stationary regime of motion of substance in a channel containing a finite number of nodes. As results of the study, we obtain a class of probability distributions connected to the amount of substance in nodes of the channel. We prove that the obtained class of distributions contains all truncated discrete probability distributions of discrete random variable ω which can take values 0,1,⋯,N. Theory for the case of a channel containing infinite number of nodes is presented in Appendix A. The continuous version of the discussed discrete probability distributions is described in Appendix B. The discussed extended model and obtained results can be used for the study of phenomena that can be modeled by flows in networks: motion of resources, traffic flows, motion of migrants, etc.     

Domino Staudinger/aza‐Wittig/Mannich Reaction: An Approach to Diversity of Di‐ and Tetrahydropyrrole Scaffolds

A highly efficient and selective domino reaction producing valuable di‐ and tetrahydropyrrole‐based skeletons from azidoethyl‐substituted CH‐acids and (thio)carbonyl compounds has been developed. By involving the additional functional groups in starting compounds into the domino reaction or postmodification of the primary reaction products, the simple construction of the pharmaceutically relevant three‐ and polycyclic azaheterocyclic scaffolds was demonstrated.     

Benchmarking of Density Functionals for the Description of Optical Properties of Newly Synthesized π-Conjugated TADF Blue Emitters

Computational modeling of the optical characteristics of organic molecules with potential for thermally activated delayed fluorescence (TADF) may assist markedly the development of more efficient emitting materials for organic light-emitting diodes. Recent theoretical studies in this area employ mostly methods from density functional theory (DFT). In order to obtain accurate predictions within this approach, the choice of a proper functional is crucial. In the current study, we focus on testing the performance of a set of DFT functionals for estimation of the excitation and emission energy and the excited singlet-triplet energy gap of three newly synthesized compounds with capacity for TADF. The emitters are designed specifically to enable charge transfer by π-electron conjugation, at the same time possessing high-energy excited triplet states. The functionals chosen for testing are from various groups ranging from gradient-corrected through global hybrids to range-separated ones. The results show that the monitored optical properties are especially sensitive to how the long-range part of the exchange energy is treated within the functional. The accurate functional should also be able to provide well balanced distribution of the π-electrons among the molecular fragments. Global hybrids with moderate (less than 0.4) share of exact exchange (B3LYP, PBE0) and the meta-GGA HSE06 are outlined as the best performing methods for the systems under study. They can predict all important optical parameters correctly, both qualitatively and quantitatively.     

Multifunctional Sulfur-Hyperdoped Silicon Nanoparticles with Engineered Mid-Infrared Sulfur-Impurity and Free-Carrier Absorption

Si nanoparticles (NPs), which are innovative promising light-harvesting components of thin-film solar cells and key-enabling biocompatible theranostic elements of infrared-laser and radiofrequency hyperthermia-based therapies of cancer cells in tumors and metastases, are significantly advanced in their near/mid-infrared band-to-band and free-carrier absorption via donor sulfur-hyperdoping during high-throughput facile femtosecond-laser ablative production in liquid carbon disulfide. High-resolution transmission electron microscopy and Raman microscopy reveal their mixed nanocrystalline/amorphous structure, enabling the extraordinary sulfur content of a few atomic percents and very minor surface oxidation/carbonization characterized by energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. A 200-nm thick layer of the nanoparticles exhibits near−mid-infrared absorbance, comparable to that of the initial 380-micron thick n-doped Si wafer (phosphor-dopant concentration ≈10¹⁵ cm⁻³), with the corresponding extinction coefficient for the hyperdoped NPs being 4–7 orders higher over the broadband spectral range of 1–25 micrometers. Such ultimate, but potentially tunable mid-IR structured, multi-band absorption of various sulfur-impurity clusters and smooth free-carrier absorption are break through advances in mid-infrared (mid-IR) laser and radiofrequency (RF) hyperthermia-based therapies, as envisioned in the RF-heating tests, and in fabrication of higher-efficiency thin-film and bulk photovoltaic devices with ultra-broad (UV−mid-IR) spectral response.     

Structure and conductivity of AOT solutions in n-hexadecane-chloroform mixtures

The structure and conductivity of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) solutions (2.5 × 10⁻⁴–2.5 × 10⁻¹ M) in n-hexadecane-chloroform mixture at the chloroform concentration from 50 to 100 vol% were studied. The diffusion ordered spectroscopy NMR study revealed that in the indicated range, the observed hydrodynamic diameter of micelles depends only on the AOT concentration and does not depend on the chloroform content. Molar fractions of free AOT molecules and those aggregated into micelles were calculated using the Lindman's law: at concentrations above 2.5 × 10⁻¹ М, the solutions contain mostly the micelles, whereas at concentrations below 2.5 × 10⁻⁴ M, the solutions contain AOT molecules. The transition region contains both the AOT molecules and the micelles. Conductivity measurements were used to determine free charge carriers in the bulk of solutions and their contributions to conductivity.