Nitrofurfural is a key building block for the synthesis of antimicrobial nitrofurans as active pharmaceutical ingredients. Its synthesis involves the nitration of furfural, a substrate derived from biobased resources. However, furfural has a delicate heteroaromatic backbone. Typical nitrations involve harsh reaction conditions, which often compromise this structure, resulting in poor reproducibility and low yields. Although acetyl nitrate, a mild nitrating agent, is suitable for this task, major deterrents remain. First, its conventional preparation method involves conditions that are not compatible with furfural. Second, significant safety concerns are associated with the unstable and explosive nature of acetyl nitrate. These critical issues are addressed herein. A safe and robust continuous flow platform featuring in situ generation of acetyl nitrate for the nitration of furfural to nitrofurfural is reported. The high level of integration and automation enables remote process operation by a single operator. Key furfural-based pharmaceutical intermediates were synthesized with favorable metrics and high reproducibility. The efficiency of this flow platform is demonstrated using a selection of best-selling nitrofuran pharmaceuticals (nifuroxazide, nifurtimox, nitrofurantoin and nitrofural), which were obtained with excellent isolated yields in under five minutes.

Despite decades of studies, a clear understanding of near-Tg phenomena remains challenging for glass-forming systems. This review delves into the intricate molecular dynamics of the small, heterocyclic thioether, 6-methyl-2,3-dihydro-1,4-benzodithiine (MeBzS2), with a particular focus on its near-Tg cold crystallization and relaxation mechanisms. Investigating isothermal crystallization kinetics at various temperatures reveals a significant interplay between its molecular dynamics and recrystallization from a supercooled liquid. We also identify two independent interconversion paths between energetically privileged conformers, characterized by strained transition states. We demonstrate that these spatial transformations induce substantial alterations in the dipole moment orientation and magnitude. Our investigation also extends to the complex salt PdCl2(MeBzS2), where we observe the transient conformers directly, revealing a direct relationship between their abundance and the local or macroscopic electric field. The initially energetically privileged isomers in an undisturbed system become less favored in the presence of an external electric field or ions, resulting even in an unexpected inversion of states. Consequently, we confirm the intramolecular character of secondary relaxation in MeBzS2 and its mechanism related to conformational changes within the heterocyclic ring. The research is based on the combination of broadband dielectric spectroscopy, X-ray diffraction, and quantum density functional theory calculations.

Molecular dynamics and transport coefficients change significantly around the so-called Arrhenius crossover in glass-forming systems. In this article, we revisit the dynamic processes occurring in a glass-forming macrocyclic crown thiaether MeBzS2O above its glass transition, revealing two crossover temperatures: TB at 309 and TA at 333 K. We identify the second one as the Arrhenius crossover that is closely related to the normal-to-supercooled liquid transition in this compound. We show that the transformation occurring at this point goes far beyond molecular dynamics (where the temperature dependence of structural relaxation times changes its character from activation-like to super-Arrhenius), being reflected also in the internal structure and diffraction pattern. In this respect, we found a twofold local organization of the nearest-neighbor molecules via weak van der Waals forces, without the formation of any medium-range order or mesophases. The nearest surrounding of each molecule evolves structurally in time due to the ongoing fast conformational changes. We identify several conformers of MeBzS2O, demonstrating that its lowest-energy conformation is preferred mainly at lower temperatures, i.e., in the supercooled liquid state. Its increased prevalence modifies locally the short-range intermolecular order and promotes vitrification. Consequently, we indicate that the Arrhenius transition is fuelled rather by conformational changes in this glass-forming macrocyclic crown thiaether, which is a different scenario from the so-far existing concepts. Our studies combine broadband dielectric spectroscopy (BDS), X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, molecular dynamics (MD) simulations, and density functional theory (DFT) calculations.

Despite years of intense investigation, calculating glass transition temperature, Tg, of non-polymeric molecules remains challenging due to many factors affecting this physical quantity. In this article, we have synthesized and thoroughly analyzed three aromatic esters of 1,2-bis(2-hydroxyethylthio)-4-methylbenzene: 1,2-bis(2-acetoxyethylthio)-4-methylbenzene, 1,2-bis(2-propionyloxyethylthio)-4-methylbenzene, and 1,2-bis(2-butyroxyethylthio)-4-methylbenzene. Utilizing differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS), we reveal that Tg of these compounds diminishes gradually as the length of the ester group increases from the two-carbon acetic to four-carbon butyric moiety, contradicting the so-far established structure - Tg relationships. We indicate that the primary origin of this unexpected trend lies in the increasing flexibility of the aromatic ring side chains. Consequently, we examine the concept of the internal plasticizing effect among low-molecular-weight glass-formers, defining it as a phenomenon, wherein the presence of a flexible substituent (particularly when attached to a rigid moiety) leads to a decrease in Tg of a non-polymeric organic compound due to hindered intermolecular packing and enhanced intramolecular dynamics. We demonstrate the universality of this theory, which goes beyond the studied set of aromatic esters, being applicable to CHN–, CHON–, CHOS-, CHNS-, and CHO-based compounds encompassing both simple van der Waals liquids and H-bonded systems. Finally, we highlight the importance of this effect for models parametrizing the structure-Tg relationship of non-polymeric glass-formers.

Latent fingerprints are a significant carrier of information for a court expert. To detect this type of forensic trace, what is necessary is a method that is easy to use, compact, and versatile. The research aimed to investigate the physicochemical properties of luminescent substances of donor–π–acceptor systems in terms of their potential use in detecting hidden fingerprints. During the research, a group of fluorene compounds consisting of the (-CH=C(CN)(COOR)) moiety was designed and successfully synthesized. The optical, electrochemical, and aggregation-induced emission properties were studied. The aggregation-induced emission of compounds has been studied in the mixture of THF (as a good solvent) and water (as a poor solvent) with different water fractions ranging from 0% to 99%. Due to the molecular structure, substances showed different affinities to organic traces. As a result, it was noticed that all compounds showed the AIE phenomenon, while during tests on latent fingerprints, it was observed that two substances had particularly forward-looking features in this field.

This article presents the synthesis and molecular dynamics investigation of three novel cyclic thioethers: 2,3-(4′-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2-ene (compound 1), 2,3,14,15-bis(4′,4″(5″)-methylbenzo)-1,4,7,10,13,16,19,22,25-octathiacyclotetracosa-2,14-diene (compound 2), and 2,3,8,9-bis(4′,4″(5″)-methylbenzo)-1,4,7,10-tetrathiacyclododeca-2,8-diene (compound 3). The compounds exhibit relatively high glass transition temperatures (Tg), which range between 254 and 283 K. This characteristic positions them within the so-far limited category of crown-like glass-formers. We demonstrate that cyclic thioethers may span both the realms of ordinary and sizeable molecular glass-formers, each featuring distinct physical properties. Furthermore, we show that the Tg follows a sublinear power law as a function of the molar mass within this class of compounds. We also reveal multiple dielectric relaxation processes of the novel cyclic thioethers. Above the Tg, their dielectric loss spectra are dominated by a structural relaxation, which originates from the cooperative reorientation of entire molecules and exhibits an excess wing on its high-frequency slope. This feature has been attributed to the Johari–Goldstein (JG) process. Each investigated compound exhibits also at least one intramolecular secondary non-JG relaxation stemming from conformational changes. Their activation energies range from approximately 19 kJ/mol to roughly 40 kJ/mol. Finally, we analyze the high-pressure molecular dynamics of compound 1, revealing a pressure-induced increase in its Tg with a dTg/dp coefficient equal to 197 ± 8 K/GPa.

In this work, the role of intermolecular interaction on the aggregation-induced emission (AIE) phenomenon and organic light-emitting diodes’ (OLEDs) performance was investigated. During the research, a group of compounds consisting of the (-CH=C(CN)(COOR)) moiety with identical energy parameters was designed using the DFT approach and successfully synthesized. The optical, electrochemical, and aggregation-induced emission properties were studied. The aggregation-induced emission of compounds has been studied in the mixture of MeCN (as a good solvent) and water (as a poor solvent) with different water fractions ranging from 0% to 99%. Moreover, the time dependence on the AIE feature was also evaluated. Thanks to their molecular structures, almost identical behavior of these substances in dilute solutions was observed. For molecules that exhibit the strong AIE phenomenon, emission efficiency increases rapidly during aggregation. What is also very interesting is it has been shown that by introducing an appropriate substituent, one can control the degree of intermolecular interactions and “control” the length of the emitted wave. Finally, OLEDs were fabricated by the spin-coating/evaporation hybrid method. Devices showed green–blueish electroluminescence (CIE coordinates: 0.107, 0.165) with maximum luminance reaching 25 cd m−2 and EQE reaching 2%.

Due to the electron-reach π -conjugated organic semiconductors system, chemical so-called p-type doping is easily achievable. Oxidation by some molecules, atoms, or ions called “ dopants ” or “ doping agents ” force the molecule to accept the positive electrical charge. In general, there are several “theoretical” ways to increase the conductivity of the semiconductors by the introduction, as mentioned above, of the charge carriers into the structure of the molecule. For this reason, it was designed and synthesized a model molecule possessing: (a) acidic hydrogen—a fragment able to undergo chemical oxidation; (b) a unit having a pi-excess ring—vulnerable to electrochemical oxidation; (c) a free electron pair—susceptible to protonation and methylation; and finally (d) a fragment that is Lewis base in nature—that is, it can form adducts with Lewis acid. In this paper, we are reporting a comprehensive study (with the aid of DFT calculation) concerning the different doping agents’ influence on physicochemical properties of the model (namely 2,5-bis(2-(2-thienyl)-thien-5-yl)thiazolo[5,4-d]thiazole) organic semiconductor.

Combination of calorimetric, dielectric, infrared, diffraction studies and quantum DFT computations was used to analyze the impact of the molecular architecture of a set of four 1-phenyl alcohols (1-phenylethanol, 1-phenyl-1-propanol, 1-phenyl-1-butanol and 2-methyl-1-phenyl-1-propanol) on their glass transition temperature, molecular dynamics, relaxation processes, hydrogen-bonding pattern and intermolecular association. We showed that all these alcohols form H-bonded supramolecular nanoassociates even at room temperature, despite containing a steric hindrance in the form of the phenyl ring in the most disfavored position. However, the concentration and the size of the H-bonded structures as well as the mutual arrangement of molecules in these clusters are tremendously affected by the molecular architecture. In linear-shaped 1-phenyl alcohols, i.e., 1-phenylethanol, 1-phenyl-1-propanol, 1-phenyl-1-butanol, the intermolecular O-H···O bonds organize themselves into chain-like patterns. Moreover, these alcohols are characterized by similar strength of intermolecular H bonds at each temperature and similar glass transition temperature. In turn, the globular molecular shape of 2-methyl-1-phenyl-1-propanol leads to a weakening of H bonds in this system, an increase in the glass transition temperature and the formation of supramolecular clusters in which O-H···O connections imply ring-like organization of molecules. Finally, these studies clearly show that unlike the glass transition temperature, the molecular dynamics of the 1-phenyl alcohols in the liquid state is not only affected by the molecular architecture and hydrogen bond strength but also by the morphology of the associates composed of H-linked molecules.

The dielectric properties, glass transition temperature and molecular dynamics of thiacrown ethers are strongly dependent on the thiacrown ring type.

PURPOSE:Three compounds obtained from ephedrine were identified and characterized by various instrumental analytical methods. Ephedrone (methcathinone) hydrochloride and its fundamental derivatives N-acetylephedrine and N-acetylephedrone were analyzed as precursors of a cathinone derivative.METHODS:The obtained samples were analyzed by gas chromatography coupled with mass spectrometry, nuclear magnetic resonance spectroscopy, infrared and Raman spectroscopy, and X-ray crystallography.RESULTS:The three compounds were confirmed as: N-methyl-2-amino-1-phenylpropan-1-one (methcathinone) hydrochloride, N-acetyl-N-methyl-2-amino-1-phenylpropan-1-one (cathinone derivative), and N-acetyl-N-methyl-2-amino-1-phenylpropan-1-ol (acetyl derivative of ephedrine).CONCLUSIONS:X-ray crystallography is especially useful for identifying the new designer drugs and their different precursor forms.

A new polymorph of sparteinium tetrachlorocuprate monohydrate [(C15H28N2)CuCl4·H2O] is reported. The structure of the analyzed crystal was solved in the orthorhombic P212121 space group with the following unit cell parameters at 295 K: a = 9.7722(2) Å; b = 13.4582(3) Å; c = 15.1582(3) Å. The various types of hydrogen bonding interactions existing in the crystal structure of this salt were compared with the data of the previously reported polymorph. XRPD measurement proved that our salt consists of a pure phase of the new polymorph. Cooling down the salt to ca. 230 K caused its color to change from orange-brown to yellow. DSC experiments revealed that during the cooling an endothermic process takes place corresponding to the mentioned color change of the salt.