Showing papers on "Solvent effects published in 2022"

Solvent Gaming Chemistry to Control the Quality of Halide Perovskite Thin Films for Photovoltaics

Abstract: Research on solvent chemistry, particularly for halide perovskite intermediates, has been advancing the development of perovskite solar cells (PSCs) toward commercial applications. A predictive understanding of solvent effects on the perovskite formation is thus essential. This work systematically discloses the relationship among the basicity of solvents, solvent-contained intermediate structures, and intermediate-to-perovskite α-FAPbI3 evolutions. Depending on their basicity, solvents exhibit their own favorite bonding selection with FA+ or Pb2+ cations by forming either hydrogen bonds or coordination bonds, resulting in two different kinds of intermediate structures. While both intermediates can be evolved into α-FAPbI3 below the δ-to-α thermodynamic temperature, the hydrogen-bond-favorable kind could form defect-less α-FAPbI3 via sidestepping the break of strong coordination bonds. The disclosed solvent gaming mechanism guides the solvent selection for fabricating high-quality perovskite films and thus high-performance PSCs and modules.

Dissecting Solvent Effects on Hydrogen Bonding

Abstract: Abstract The experimental isolation of H‐bond energetics from the typically dominant influence of the solvent remains challenging. Here we use synthetic molecular balances to quantify amine/amide H‐bonds in competitive solvents. Over 200 conformational free energy differences were determined using 24 H‐bonding balances in 9 solvents spanning a wide polarity range. The correlations between experimental interaction energies and gas‐phase computed energies exhibited wild solvent‐dependent variation. However, excellent correlations were found between the same computed energies and the experimental data following empirical dissection of solvent effects using Hunter's α/β solvation model. In addition to facilitating the direct comparison of experimental and computational data, changes in the fitted donor and acceptor constants reveal the energetics of secondary local interactions such as competing H‐bonds.

Solvent Effects on the Menshutkin Reaction

Abstract: The Menshutkin reaction is a methyl transfer reaction relevant in fields ranging from biochemistry to chemical synthesis. In the present work, the energetics and solvent distributions for NH3+MeCl and Pyr+MeBr reactions were investigated in explicit solvent (water, methanol, acetonitrile, benzene, cyclohexane) by means of reactive molecular dynamics simulations. For polar solvents (water, methanol, and acetonitrile) and benzene, strong to moderate catalytic effects for both reactions were found, whereas apolar and bulky cyclohexane interacts weakly with the solute and does not show pronounced barrier reduction. The calculated barrier heights for the Pyr+MeBr reaction in acetonitrile and cyclohexane are 23.2 and 28.1 kcal/mol compared with experimentally measured barriers of 22.5 and 27.6 kcal/mol, respectively. The solvent distributions change considerably between reactant and TS but comparatively little between TS and product conformations of the solute. As the system approaches the transition state, correlated solvent motions occur which destabilize the solvent-solvent interactions. This is required for the system to surmount the barrier. Finally, it is found that the average solvent-solvent interaction energies in the reactant, TS, and product state geometries are correlated with changes in the solvent structure around the solute.

Solvent effect on ESIPT process of N-(8-Quinolyl) salicylaldimine: a DFT/TD-DFT calculation

Abstract: The investigations of the solvent effect on ESIPT process of N-(8-Quinolyl) salicylaldimine (QS) are carried out using DFT and TD-DFT methods. We choice TOL, THF, ACE and DMSO solvents to simulate the experimental solvent conditions. The normal and tautomeric structures of the QS in the S0 and S1 states are optimized by means of DFT and TD-DFT method in four different kinds of solvents. Through the analysis of the critical geometrical parameters related to hydrogen bond interactions, it could be found that QS molecule preform to be planar or nearly planar in the S1 state, and more importantly, the excited-state hydrogen bond is strengthened. By comparing IR vibrational spectra, RDG isosurfaces and scatter graphs in the four solvent conditions, we found that the hydrogen bond is strengthen after photoexcitation, and weakened with the increase of the dielectric constant of the solvents. The calculated absorption and fluorescence spectra are basically agreement with existing evidence from previous experiment. The energy barriers of ground and excited states of QS molecule under the different solvent conditions have been analyzed by established potential energy curves (PECs) in the S0 and S1 states, and the corresponding energy barriers are increased with the effect of change from TOL to DMSO solvents. Therefore, with the increasing dielectric constant of solvents, the ESIPT become favored.

Solvation of the Boc-Val-Phe-nPr peptide characterized by VCD spectroscopy and DFT calculations.

Abstract: The conformational preferences of peptides are strongly determined by hydrogen bonding interactions. Intermolecular solute-solvent interactions compete with intramolecular interactions, which typically stabilize the secondary structure of the peptide. The analysis of vibrational circular dichroism (VCD) spectra can give insights into solvation-induced changes in the conformational distribution of small peptides. Here we describe the VCD spectroscopic characterization of the model peptide Boc-Val-Phe-nPr in chloroform as representative for a weakly interacting solvent and dimethyl sulfoxide (DMSO-d6) as a strongly hydrogen bonding solvent. We show that the conformational preferences of the peptide in chloroform are well-described by the computationally predicted distribution of the isolated molecule assuming only implicit solvation effects through a continuum solvation model. In order to simulate the spectra recorded in DMSO-d6, solvation was accounted for explicitly by computed microsolvated structures containing one to three solvent molecules. A good match of the computed spectra with the experimental data is obtained by this method. Comparing the conformational distributions in deuterated chloroform-d1 and DMSO-d6, structures with intramolecular hydrogen bonds such as the (δ,δ)-conformer family contribute to the conformational distribution only when there is no strong interaction with the solvent. This is in contrast to the results for the related Boc-Pro-Phe-nPr studied before, for which the intramolecular interaction was found to persist in DMSO-d6. Furthermore, we discuss the influence of hydrogen bonding to different numbers of solvent molecules on the spectral signatures and show that the structure of the peptide in DMSO-d6 is best described as a mixture of twofold-solvated (δ,β)- and threefold-solvated (β,β)-conformers.

Solvent coordination to palladium can invert the selectivity of oxidative addition

Abstract: Reaction solvent was previously shown to influence the selectivity of Pd/P t Bu3-catalyzed Suzuki-Miyaura cross-couplings of chloroaryl triflates. The role of solvents has been hypothesized to relate to their polarity, whereby polar solvents stabilize anionic transition states involving [Pd(P t Bu3)(X)]- (X = anionic ligand) and nonpolar solvents do not. However, here we report detailed studies that reveal a more complicated mechanistic picture. In particular, these results suggest that the selectivity change observed in certain solvents is primarily due to solvent coordination to palladium. Polar coordinating and polar noncoordinating solvents lead to dramatically different selectivity. In coordinating solvents, preferential reaction at triflate is likely catalyzed by Pd(P t Bu3)(solv), whereas noncoordinating solvents lead to reaction at chloride through monoligated Pd(P t Bu3). The role of solvent coordination is supported by stoichiometric oxidative addition experiments, density functional theory (DFT) calculations, and catalytic cross-coupling studies. Additional results suggest that anionic [Pd(P t Bu3)(X)]- is also relevant to triflate selectivity in certain scenarios, particularly when halide anions are available in high concentrations.

The quantum chemical solvation of indole: accounting for strong solute-solvent interactions using implicit/explicit models.

Abstract: In this paper, we investigate the efficacy of different quantum chemical solvent modelling methods of indole in both water and methylcyclohexane solutions. The goal is to show that one can yield good photophysical properties in strongly coupled solute-solvent systems using standard DFT methods. We use standard and linearly-corrected Polarisable Continuum Models (PCM), as well as explicit solvation models, and compare the different model parameters, including the choice of density functional, basis set, and number of explicit solvent molecules. We demonstrate that implicit models overestimate energies and oscillator strengths. In particular, for indole-water, no level inversion is observed, suggesting a dielectric medium on its own is insufficient. In contrast, energies are seen to converge fairly rapidly with respect to cluster size towards experimentally measured properties in the explicit models. We find that the use of B3LYP with a diffuse basis set can adequately represent the photophysics of the system with a cluster size of between 9-12 explicit water molecules. Sampling of configurations from a molecular dynamics simulation suggests that the single point results are suitably representative of the solvated ensemble. For indole-water, we show that solvent reorganisation plays a significant role in stabilisation of the excited state energies. It is hoped that the findings and observations of this study will aid in the choice of solvation model parameters in future studies.

Solvent Selective Effect Occurs in Iodinated Adamantanone Ferroelectrics

Abstract: Organic ferroelectrics, as a type of crystalline compound, are generally solution processing. However, for most crystalline compounds, the changing of solvent would not influence the crystalline phase, let alone their physical performance. Here, the solvent selective effect occurs in the iodinated adamantanone ferroelectrics. By changing the solvent with different polarities, the ferroelectric crystals can be induced in two different phases, which is unprecedented to the knowledge. More strikingly, this solvent‐induced transformation could realize the physical performance optimization in the orthorhombic phase (orth‐I‐OA, obtained from ethanol) with a stronger second harmonic generation (SHG) response, greater piezoelectric coefficient d33 of 5 pC N−1, and larger spontaneous polarization (Ps) of 3.43 µC cm−2 than those of monoclinic one (mono‐I‐OA, obtained from ethyl acetate). Such an intriguing phenomenon might be closely related to solvent polarity. Based on the quantitative and qualitative analyses, the similar interaction energies of these two phases suggest that their transformation could be easily realized via changing the solvent. This work provides new insights into the chemical design and performance optimization of organic ferroelectrics.

Solvent Etching Process for Graphitic Carbon Nitride Photocatalysts Containing Platinum Cocatalyst: Effects of Water Hydrolysis on Photocatalytic Properties and Hydrogen Evolution Behaviors

Abstract: In this study, we synthesized Pt/g-C3N4 photocatalysts modified by a solvent etching process where ethanol (Pt/CN0), water (Pt/CN100), and a 50:50 mixture (Pt/CN50) were used as a solvent, and investigated the optimal properties of g-C3N4 to prepare the best Pt/g-C3N4 for photocatalytic hydrogen evolution. From diverse characterizations, water was proven to be a stronger solvent agent, resulting in not only the introduction of more O-functional groups onto the g-C3N4 surface, but also the degradation of a regular array of tri-s-triazine units in the g-C3N4 structure. While the addition of O-functional groups positively influenced the oxidation state of the Pt cocatalyst and the hydrogen production rate, the changes to g-C3N4 structure retarded charge transfer on its surface, inducing negative effects such as fast recombination and less oxidized Pt species. Pt/CN50 that was synthesized with the 50:50 solvent mixture exhibited the highest hydrogen production rate of 590.9 µmol g−1h−1, while the hydrogen production rates of Pt/CN0 (with pure ethanol solvent) and Pt/CN100 (with pure water solvent) were 462.7, and 367.3 µmol g−1h−1, respectively.

Predicting Solvent Effects on SN2 Reaction Rates: Comparison of QM/MM, Implicit, and MM Explicit Solvent Models.

Abstract: Solvents are one of the key variables in the optimization of a synthesis yield or properties of a synthesis product. In this paper, contemporary solvent models are applied to predict the rates of SN2 reactions in a range of aqueous and non-aqueous solvents. High-level CCSD(T)/CBS//M06-2X/6-31+G(d) gas phase energies were combined with solvation free energies from SMD, SM12, and ADF-COSMO-RS continuum solvent models, as well as molecular mechanics (MM) explicit solvent models with different atomic charge schemes to predict the rate constants of three SN2 reactions in eight protic and aprotic solvents. It is revealed that the prediction of rate constants in organic solvents is not necessarily less challenging than in water and popular solvent models struggle to predict their rate constants to within 3 log units of experimental values. Among the continuum solvent models, the ADF-COSMO-RS model performed the best in predicting absolute rate contants while the SM12 model was best at predicting relative rate constants with an average accuracy of about 1.5 and 0.8 log units, respectively. The use of computationally more demanding MM explicit solvent models did not translate to improvements in absolute rate constants but was quite effective at predicting relative rate constants due to systematic error cancellation. Free energy barriers obtained from umbrella sampling with explicit solvent QM/MM simulations led to excellent agreement with experimental values, provided that a validated level of theory is used to treat the QM region.

Effect of solvent motions on the dynamics of the Diels–Alder reaction

Abstract: How solvent motions affect the dynamics of chemical reactions in which the solute undergoes a substantial shape change is a fundamental but elusive issue. This work utilizes reactive simulation and Grote-Hynes theory to explore the effect of solvent motions on the dynamics of the Diels-Alder reaction (in the reverse direction, this reaction involves very substantial solute expansion) in aprotic solvents. The results reveal that the solvent environment is not sufficiently constraining to influence transition state passage dynamics, with the calculated transmission coefficients being close to unity. Even when solvent motions are suppressed or artificially slowed down, the solvent only affects the reaction dynamics in the transition state region to a very small extent. The only notable effect of solvent occurs far from the transition state region and corresponds to caging of the reactants within the reactant well.

Degradation Kinetics and Solvent Effects of Various Long-Chain Quaternary Ammonium Salts

Abstract: Surfactants such as quaternary ammonium salts (QAS) have been in increasing demand, for emerging new applications. Recent attempts at process intensification oftheir production, have disclosed the need for a better understanding of QAS thermal stability. This work aims to determine degradation kinetics of various QASs, and theassociated solvent effects. Degradation kinetics of four methyl carbonate QASs were determined in variouspolar solvents in stainless steel batch autoclaves. 1H NMR spectrometry was employed for online analysis of the reaction mixtures. The kinetic parameters were then usedto compare the thermal stability of the four compounds in the polar solvents. Water showed not degradation, and methanol (MeOH) was the solvent that provided thesecond-best stability. Water-MeOH mixtures may provide an overall optimum. More, and longer long-chain substituents increased the degradation rate. Thermogravimetric Analysis was used to obtain the thermal stability in a solid-state, i.e. solventless environment. Isoconversional analysis showed that no reliable kinetic parameters could be determined. Nevertheless, the data did allow for a compar-ison of the thermal stability of 14 different QASs. Furthermore, the relative instability of the compounds in solid-state demonstrated the challenges of solventless QAS production.