High-Pressure and Temperature Effects on the Clustering Ability of Monohydroxy Alcohols.

This study examined the clustering behavior of monohydroxy alcohols, where hydrogen-bonded clusters of up to a hundred molecules on the nanoscale can form. By performing X-ray diffraction experiments at different temperatures and under high pressure, we investigated how these conditions affect the ability of alcohols to form clusters. The pioneering high-pressure experiment performed on liquid alcohols contributes to the emerging knowledge in this field. Implementation of molecular dynamics simulations yielded excellent agreement with the experimental results, enabling the analysis of theoretical models. Here we show that at the same global density achieved either by alteration of pressure or temperature, the local aggregation of molecules at the nanoscale may significantly differ. Surprisingly, high pressure not only promotes the formation of hydrogen-bonded clusters but also induces the serious reorganization of molecules. This research represents a milestone in understanding association under extreme thermodynamic conditions in other hydrogen bonding systems such as water.

Revisiting Dynamic Processes and Relaxation Mechanisms in a Heterocyclic Glass-Former: Direct Observation of a Transient State.

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.

Pressure-Induced Aggregation of Associating Liquids as a Driving Force Enhancing Hydrogen Bond Cooperativity.

The behavior of hydrogen bonds under extreme pressure is still not well understood. Until now, the shift of the stretching vibration band of the X-H group (X = the donor atom) in infrared spectra has been attributed to the variation in the length of the covalent X-H bond. Herein, we combined infrared spectroscopy and X-ray diffraction experimental studies of two H-bonded liquid hexane derivatives, i.e., 2-ethyl-1-hexanol and 2-ethyl-1-hexylamine, in diamond anvil cells at pressures up to the GPa level, with molecular dynamics simulations covering similar thermodynamic conditions. Our findings revealed that the observed changes in the X-H stretching vibration bands under compression are not primarily due to H-bond shortening resulting from increased density but mainly due to cooperative enhancement of H-bonds caused by intensified molecular clustering. This sheds new light on the nature of H-bond interactions and the structure of liquid molecular systems under compression.

Molecular Dynamics and Near-Tg Phenomena of Cyclic Thioethers.

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.

Experimental and Computational Approach to Studying Supramolecular Structures in Propanol and Its Halogen Derivatives.

A series of four alcohols, n-propanol and its halogen (Cl, Br, and I) derivatives, were selected to study the effects of variation in polarity and halogen-driven interactions on the hydrogen bonding pattern and supramolecular structure by means of experimental and theoretical methods. It was demonstrated on both grounds that the average strength of H-bonds remains the same but dissociation enthalpy, the size of molecular nanoassemblies, as well as long-range correlations between dipoles vary with the molecular weight of halogen atom. Further molecular dynamics simulations indicated that it is connected to the variation in the molecular order introduced by specific halogen-based hydrogen bonds and halogen-halogen interactions. Our results also provided important experimental evidence supporting the assumption of the transient chain model on the molecular origin of the structural process in self-assembling alcohols.

Computer simulations as an effective way to distinguish supramolecular nanostructure in cyclic and phenyl alcohols.

Molecular dynamics simulations supported by x-ray-diffraction experimental data were utilized to demonstrate how replacing the cyclic ring with the phenyl one in molecules of alcohols significantly differentiates their nanostructure by reducing the number of H-bonded clusters. Besides, molecules in the phenyl alcohols associate themselves in clusters via phenyl ring organization which likely is the result of OH⋯π and π⋯π interactions. Thus, at room temperature, the supramolecular structure of phenyl alcohols is more heterogeneous and governed by the formation of various clusters arising due to three types of interactions, while in cyclic alcohols, the H bonding controls the association of molecules. We believe that our methodology could be applied to better understand the fundamental process of association via H bonding and the competitive aggregation caused by phenyl rings.

A study of OH···O hydrogen bonds along various isolines in 2-ethyl-1-hexanol. Temperature or pressure - which parameter controls their behavior?

The nature of H-bonding interactions is still far from being understood despite intense experimental and theoretical studies on this subject carried out by the leading research centers. In this paper, by a combination of unique high-pressure infrared, dielectric and volumetric data, the intramolecular dynamics of hydroxyl moieties (which provides direct information about H-bonds) was studied along various isolines, i.e., isotherms, isobars, isochrones, and isochores, in a simple monohydroxy alcohol (2-ethyl-1-hexanol). This allowed us to discover that the temperature controls the intermolecular hydrogen bonds, which then affect the intramolecular dynamics of OH units. Although the role of density fluctuations gets stronger as temperature rises. We also demonstrated a clear connection between the intra- and intermolecular dynamics of the associating liquid at high pressure. The data reported herein open a new perspective to explore this important aspect of the glass transition phenomenon and understand H-bonding interactions at varying thermodynamic conditions.

How differences in the molecular structure of monohydroxy alcohols affect the tendency to crystallization.

The tendency to crystallize was studied in the selected monohydroxy alcohols: 1-chloro-2-methyl-2-propanol, 1-chloro-2-propanol, 3-chloro-1-propanol, and 8-chloro-1-octanol. Performed calorimetric measurements have proved that the differences in structures of tested alcohols influence the tendency to crystallization. At a sufficiently fast heating rate, no crystallization was observed in the case of 1-chloro-2-propanol and 3-chloro-1-propanol, contrary to other two alcohols. The obtained results suggest that elongation of the alkyl chain or adding a methyl group to the hydrocarbon backbone increases the susceptibility to crystallization.

Supramolecular Structure of Phenyl Derivatives of Butanol Isomers.

Wide-angle X-ray scattering patterns were recorded for a series of aliphatic butanol isomers (n-, iso-, sec-, tert-butanol) and their phenyl derivatives (4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, 4-phenyl-2-butanol, and 2-methyl-1-phenyl-2-propanol, respectively) to determine their atomic-scale structure with particular emphasis on the formation of supramolecular clusters. In addition, molecular dynamics simulations were carried out and yielded good agreement with experimental data. The combination of experimental and theoretical results allowed clarification of the origin of the pre-peak appearing at low scattering angles for the aliphatic butanols and its absence for their phenyl counterparts. It was demonstrated that the location of the hydroxyl group in the molecule of alkyl butanol, its geometry, and rigidity determine the morphology of the supramolecular clusters, while the addition of the aromatic moiety causes more disordered organization of molecules. The phenyl group significantly decreases the number of hydrogen bonds and size of the supramolecular clusters formed via the O-H···O scheme. The lower association ability of phenyl alcohols via H-bonds is additionally attenuated by the appearance of competing π-π configurations evidenced by the structural models.

Simple Rules for Complex Near-Glass-Transition Phenomena in Medium-Sized Schiff Bases.

Glass-forming ability is one of the most desired properties of organic compounds dedicated to optoelectronic applications. Therefore, finding general structure-property relationships and other rules governing vitrification and related near-glass-transition phenomena is a burning issue for numerous compound families, such as Schiff bases. Hence, we employ differential scanning calorimetry, broadband dielectric spectroscopy, X-ray diffraction and quantum density functional theory calculations to investigate near-glass-transition phenomena, as well as ambient- and high-pressure molecular dynamics for two structurally related Schiff bases belonging to the family of glycine imino esters. Firstly, the surprising great stability of the supercooled liquid phase is shown for these compounds, also under high-pressure conditions. Secondly, atypical self-organization via bifurcated hydrogen bonds into lasting centrosymmetric dimers is proven. Finally, by comparing the obtained results with the previous report, some general rules that govern ambient- and high-pressure molecular dynamics and near-glass transition phenomena are derived for the family of glycine imino esters. Particularly, we derive a mathematical formula to predict and tune their glass transition temperature (Tg) and its pressure coefficient (dTg/dp). We also show that, surprisingly, despite the presence of intra- and intermolecular hydrogen bonds, van der Waals and dipole-dipole interactions are the main forces governing molecular dynamics and dielectric properties of glycine imino esters.

Effect of Gd3+ Substitution on Thermoelectric Power Factor of Paramagnetic Co2+-Doped Calcium Molybdato-Tungstates.

A series of Co2+-doped and Gd3+-co-doped calcium molybdato-tungstates, i.e., Ca1-3x-yCoyxGd2x(MoO4)1-3x(WO4)3x (CCGMWO), where 0 < x ≤ 0.2, y = 0.02 and represents vacancy, were successfully synthesized by high-temperature solid-state reaction method. XRD studies and diffuse reflectance UV-vis spectral analysis confirmed the formation of single, tetragonal scheelite-type phases with space group I41/a and a direct optical band gap above 3.5 eV. Magnetic and electrical measurements showed insulating behavior with n-type residual electrical conductivity, an almost perfect paramagnetic state with weak short-range ferromagnetic interactions, as well as an increase of spin contribution to the magnetic moment and an increase in the power factor with increasing gadolinium ions in the sample. Broadband dielectric spectroscopy measurements and dielectric analysis in the frequency representation showed a relatively high value of dielectric permittivity at low frequencies, characteristic of a space charge polarization and small values of both permittivity and loss tangent at higher frequencies.

Phenyl Ring: A Steric Hindrance or a Source of Different Hydrogen Bonding Patterns in Self-Organizing Systems?

A series of five alcohols (3-methyl-2-butanol, 1-cyclopropylethanol, 1-cyclopentylethanol, 1-cyclohexylethanol, and 1-phenylethanol) was used to study the impact of the size of steric hindrance and its aromaticity on self-assembling phenomena in the liquid phase. In this Letter, we have explicitly shown that the phenyl ring exerts a much stronger effect on the self-organization of molecules via the O-H···O scheme than any other type of steric hindrance, leading to a significant decline in the size and concentration of the H-bonded clusters. Given the combination of calorimetric, dielectric, infrared, and diffraction studies, this phenomenon was ascribed to its additional proton-acceptor function for the competitive intermolecular O-H···π interactions. The consequence of this is a different packing of molecules on the short- and medium-range scale.

Conformational analysis and molecular dynamics of glass-forming aromatic thiacrown ethers.

In this work, we report the synthesis, unexpected glass-forming properties, molecular dynamics and conformational analysis of two thiacrown ethers: 6-methyl-2,3-dihydro-1,4-benzodithiine (1), with a six-membered heterocyclic ring, and macrocyclic 2,3-(4'-methylbenzo)-1,4-dithia-7-oxacyclononane (2). Based on the calorimetric studies, we showed that compound 1 is a viscous liquid at room temperature undergoing vitrification at 192 K. Compound 2 is a crystalline solid at room temperature characterized by a melting point at 331 K; however, it can be vitrified with ease after being melted by cooling down to 224 K. This gave us the unique possibility to analyze the dielectric response and to follow the molecular dynamics in supercooled liquid and glassy states for each thiacrown ether. Two relaxation processes were found for compound 1, which are structural α-relaxation, connected with the collective rotational motions of molecules in a liquid, and a low-temperature secondary γ-process, resulting from conformational changes in the heterocyclic ring. Beside these two relaxation processes, an additional intermolecular ß-process of JG type was detected in the case of compound 2. Finally, based on the analysis of the thermal evolution of the Kirkwood-Fröhlich factor, it has also been shown that thiacrown ethers may be characterized by a local ordering between neighboring molecules in the supercooled liquid state.

Density Scaling Based Detection of Thermodynamic Regions of Complex Intermolecular Interactions Characterizing Supramolecular Structures.

In this paper, applying the density scaling idea to an associated liquid 4-methyl-2-pentanol used as an example, we identify different pressure-volume-temperature ranges within which molecular dynamics is dominated by either complex H-bonded networks most probably leading to supramolecular structures or non-specific intermolecular interactions like van der Waals forces. In this way, we show that the density scaling law for molecular dynamics near the glass transition provides a sensitive tool to detect thermodynamic regions characterized by intermolecular interactions of different type and complexity for a given material in the wide pressure-volume-temperature domain even if its typical form with constant scaling exponent is not obeyed. Moreover, we quantify the observed decoupling between dielectric and mechanical relaxations of the material in the density scaling regime. The suggested methods of analyses and their interpretations open new prospects for formulating models based on proper effective intermolecular potentials describing physicochemical phenomena near the glass transition.

Dipole Relaxation in Semiconducting Zn2-xMgxInV3O11 Materials (Where x = 0.0, 0.4, 1.0, 1.6, and 2.0).

This paper reports on the electrical and broadband dielectric spectroscopy studies of Zn2-xMgxInV3O11 materials (where x = 0.0, 0.4, 1.0, 1.6, 2.0) synthesized using a solid-state reaction method. These studies showed n-type semiconducting properties with activation energies of 0.147-0.52 eV in the temperature range of 250-400 K, symmetric and linear I-V characteristics, both at 300 and 400 K, with a stronger carrier emission for the matrix and much less for the remaining samples, as well as the dipole relaxation, which was the slowest for the sample with x = 0.0 (matrix) and was faster for Mg-doped samples with x > 0.0. The faster the dipole relaxation, the greater the accumulation of electric charge. These effects were analyzed within a framework of the DC conductivity and the Cole-Cole fit function, including the solid-state density and porosity of the sample. The resistivity vs. temperature dependence was well fitted using the parallel resistor model. Our ab initio calculations also show that the bandgap increased with the Mg content.

APEX Strategy Represented by Diels-Alder Cycloadditions-New Opportunities for the Syntheses of Functionalised PAHs.

Diels-Alder cycloaddition of various dienophiles to the bay region of polycyclic aromatic hydrocarbons (PAHs) is a particularly effective and useful tool for the modification of the structure of PAHs and thereby their final properties. The Diels-Alder cycloaddition belongs to the single-step annulative π-extension (APEX) reactions and represents the maximum in synthetic efficiency for the constructions of π-extended PAHs including functionalised ones, nanographenes, and π-extended fused heteroarenes. Herein we report new applications of the APEX strategy for the synthesis of derivatives of 1,2-diarylbenzo[ghi]perylene, 1,2-diarylbenzo[ghi]perylenebisimide and 1,2-disubstituted-benzo[j]coronene. Namely, the so far unknown cycloaddition of 1,2-diarylacetylenes into the perylene and perylenebisimide bay regions was used. 1,2-Disubstituted-benzo[j]coronenes were obtained via cycloaddition of benzyne into 1,2-diarylbenzo[ghi]perylenes by using a new highly effective system for benzyne generation and/or high pressure conditions. Moreover, we report an unprecedented Diels-Alder cycloaddition-cycloaromatisation domino-type reaction between 1,4-(9,9-dialkylfluoren-3-yl)-1,3-butadiynes and perylene. The obtained diaryl-substituted core-extended PAHs were characterised by DFT calculation as well as electrochemical and spectroscopic measurements.

Effect of Flexibility and Nanotriboelectrification on the Dynamic Reversibility of Water Intrusion into Nanopores: Pressure-Transmitting Fluid with Frequency-Dependent Dissipation Capability.

In this article, the effect of a porous material's flexibility on the dynamic reversibility of a nonwetting liquid intrusion was explored experimentally. For this purpose, high-pressure water intrusion together with high-pressure in situ small-angle neutron scattering were applied for superhydrophobic grafted silica and two metal-organic frameworks (MOFs) with different flexibility [ZIF-8 and Cu2(tebpz) (tebpz = 3,3',5,5'tetraethyl-4,4'-bipyrazolate)]. These results established the relation between the pressurization rate, water intrusion-extrusion hysteresis, and porous materials' flexibility. It was demonstrated that the dynamic hysteresis of water intrusion into superhydrophobic nanopores can be controlled by the flexibility of a porous material. This opens a new area of applications for flexible MOFs, namely, a smart pressure-transmitting fluid, capable of dissipating undesired vibrations depending on their frequency. Finally, nanotriboelectric experiments were conducted and the results showed that a porous material's topology is important for electricity generation while not affecting the dynamic hysteresis at any speed.

Glassy dynamics predicted by mutual role of free and activation volumes.

Broadband Dielectric Spectroscopy (BDS) at elevated pressures and Positron Annihilation Lifetime Spectroscopy (PALS) are employed to elucidate the importance of the ratio of activation and free volumes during vitrification. We show that this ratio has a linear correlation with the structural relaxation of glass forming liquids in a wide temperature range hence engendering it as a vital input in the description of the dynamic glass transition.

Inflection point in the Debye relaxation time of 2-butyl-1-octanol.

We report a striking anomaly in the pressure dependent Debye-relaxation time of the branched monohydroxy alcohol 2-butyl-1-octanol. Evidence of a crossover from slower to faster than exponential pressure dependency was obtained at different temperatures via high pressure broadband dielectric spectroscopy. At the same time, viscosity measurements reveal similar behavior in the viscosity, respectively, the structural relaxation time, indicating a similar origin of the phenomena.

Breakdown of the Simple Arrhenius Law in the Normal Liquid State.

It is common practice to discuss the temperature effect on molecular dynamics of glass formers above the melting temperature in terms of the Arrhenius law. Using dielectric spectroscopy measurements of dc conductivity and structural relaxation time on the example of the typical glass former propylene carbonate, we provide experimental evidence that this practice is not justified. Our conclusions are supported by employing thermodynamic density scaling and the occurrence of inflection points in isothermal dynamic data measured at elevated pressure. Additionally, we propose a more suitable approach to describe the dynamics both above and below the inflection point based on a modified MYEGA model.