Showing papers on "Solvent effects published in 2021"

Observation of Transition from Ferroelasticity to Ferroelectricity by Solvent Selective Effect in Anilinium Bromide.

Abstract: Organic ferroelectrics are highly desirable for their lightweight, mechanical flexibility and biocompatibility. However, the rational design of organic ferroelectrics has always been faced with great challenges. Anilinium bromide (AB) has two structures reported in the Cambridge Crystallographic Data Centre, which might be an mmm F2/ m type ferroelastic (AB-1). When we studied its ferroelasticity, we were surprised to discover that there was another crystal (AB-2) in H 2 O besides this one, and they were very difficult to separate. By changing the solvent, we found that AB-1 crystals could be formed in ethanol, where ferroelastic domains were visualized by polarized light microscopy, and AB-2 crystals could be obtained from various crystallisation solvents of methanol, isopropanol, N -butanol, acetonitrile, dimethyl sulphoxide, and N , N -dimethylformamide, which undergo a ferroelectric phase transition with mm 2F m , showing clear ferroelectricity in two phases. To our knowledge, the regulation of ferroelasticity to ferroelectricity by solvent selective effect is unprecedented in the field of ferroelectrics. This work offers an efficient exploratory path to enriching the family of organic ferroelectrics, and should inspire further exploration of the interplay between solvent effect and physical properties.

Critical role of solvent-modulated hydrogen-binding strength in the catalytic hydrogenation of benzaldehyde on palladium

Abstract: Solvents not only disperse reactants to enhance mass transport in catalytic reactions but also alter the reaction kinetically. Here, we show that the rate of benzaldehyde hydrogenation on palladium differs by up to one order of magnitude in different solvents (dioxane < tetrahydrofuran < water < methanol). However, the reaction pathway does not change; the majority of turnovers occurs by stepwise addition of sorbed hydrogen to sorbed benzaldehyde, first to the carbonyl oxygen and then to the carbon atom of the formyl group, forming benzyl alcohol. An analysis of the solvation energies shows that both ground and transition states are destabilized by the solvents compared to those at the gas–solid interface. The destabilization extent of the reacting organic substrates in both states are similar and, therefore, compensate each other, making the net kinetic effects inconsequential. Instead, the marked reactivity differences arise only from the differences in the solvation of sorbed hydrogen. Solvent effects play major roles in determining the mechanism of catalytic reactions, but their understanding remains often qualitative. Here, the authors provide a quantitative analysis of the effect of solvents on the catalytic hydrogenation of benzaldehyde on palladium, revealing the solvents’ crucial role in modulating the hydrogen-binding strength.

Machine learning of solvent effects on molecular spectra and reactions.

Abstract: Fast and accurate simulation of complex chemical systems in environments such as solutions is a long standing challenge in theoretical chemistry. In recent years, machine learning has extended the boundaries of quantum chemistry by providing highly accurate and efficient surrogate models of electronic structure theory, which previously have been out of reach for conventional approaches. Those models have long been restricted to closed molecular systems without accounting for environmental influences, such as external electric and magnetic fields or solvent effects. Here, we introduce the deep neural network FieldSchNet for modeling the interaction of molecules with arbitrary external fields. FieldSchNet offers access to a wealth of molecular response properties, enabling it to simulate a wide range of molecular spectra, such as infrared, Raman and nuclear magnetic resonance. Beyond that, it is able to describe implicit and explicit molecular environments, operating as a polarizable continuum model for solvation or in a quantum mechanics/molecular mechanics setup. We employ FieldSchNet to study the influence of solvent effects on molecular spectra and a Claisen rearrangement reaction. Based on these results, we use FieldSchNet to design an external environment capable of lowering the activation barrier of the rearrangement reaction significantly, demonstrating promising venues for inverse chemical design.

Solvent Effects in Supramolecular Chemistry: Linear Free Energy Relationships for Common Intermolecular Interactions.

Abstract: The proper choice of solvent is of major importance for all studies in supramolecular chemistry, including molecular recognition in host-guest systems, intramolecular folding, self-assembly, and supramolecular polymerization. In this Perspective, the usefulness of linear free energy relationships (LFERs) is highlighted to unravel the effect of solvents on coordinate bonding (e.g., cation-crown ether), hydrogen bonding, halogen bonding, dipolar aggregation, and π-π-stacking. For all of these intermolecular interactions widely applied in supramolecular systems, LFER relationships between the Gibbs binding energies and common solvent polarity scales including ET(30), π*, α or β based on solvatochromic dyes, scales derived from binding processes such as Gutmann donor and acceptor numbers or hydrogen bond donor and acceptor scales, or physical functions like the Kirkwood-Onsager or the Liptay-Onsager functions could be demonstrated. These relationships can now be applied toward a better understanding of the prevailing intermolecular forces for supramolecular interactions. They further enable a rational selection of the most suitable solvent for the preparation of self-assembled materials and the estimation of binding constants without the need for time-consuming comprehensive investigations of solvents.

Machine learning implicit solvation for molecular dynamics.

Abstract: Accurate modeling of the solvent environment for biological molecules is crucial for computational biology and drug design. A popular approach to achieve long simulation time scales for large system sizes is to incorporate the effect of the solvent in a mean-field fashion with implicit solvent models. However, a challenge with existing implicit solvent models is that they often lack accuracy or certain physical properties compared to explicit solvent models as the many-body effects of the neglected solvent molecules are difficult to model as a mean field. Here, we leverage machine learning (ML) and multi-scale coarse graining (CG) in order to learn implicit solvent models that can approximate the energetic and thermodynamic properties of a given explicit solvent model with arbitrary accuracy, given enough training data. Following the previous ML–CG models CGnet and CGSchnet, we introduce ISSNet, a graph neural network, to model the implicit solvent potential of mean force. ISSNet can learn from explicit solvent simulation data and be readily applied to molecular dynamics simulations. We compare the solute conformational distributions under different solvation treatments for two peptide systems. The results indicate that ISSNet models can outperform widely used generalized Born and surface area models in reproducing the thermodynamics of small protein systems with respect to explicit solvent. The success of this novel method demonstrates the potential benefit of applying machine learning methods in accurate modeling of solvent effects for in silico research and biomedical applications.

Different view of solvent effect on the synthesis methods of zeolitic imidazolate framework-8 to tuning the crystal structure and properties

Abstract: One of the important aims in the synthesis of zeolite imidazolate framework-8 is to prepare crystals with predictable structures and valuable properties. It is observed that the properties of ZIF-8 have been directly or indirectly determined by various synthetic factors. Among many synthetic factors, solvents and synthesis methods are unavoidable parameters that control the overall structure of ZIF-8. This article presents a deep understanding of how solvents play their role in the crystallization and structure and therefore the properties of ZIF-8 by considering the polarity, viscosity, interfacial tension and molecular structure and comparing the behaviour of each solvent in every synthesis method. Also, to clearly realize their effect on the formation and final properties of ZIF-8, the crystallization process and mass transfer are discussed.

Theoretical investigations on the HOMO–LUMO gap and global reactivity descriptor studies, natural bond orbital, and nucleus-independent chemical shifts analyses of 3-phenylbenzo[d]thiazole-2(3H)-imine and its para-substituted derivatives: Solvent and substituent effects

Abstract: Natural bond orbital analysis, salvation, and substituent effects of electron-releasing (–CH3, –OH) and electron-withdrawing (–Cl, –NO2, –CF3) groups at para positions on the molecular structure of

Quantifying Uncertainties in Solvation Procedures for Modeling Aqueous Phase Reaction Mechanisms.

Abstract: Computational quantum chemistry provides fundamental chemical and physical insights into solvated reaction mechanisms across many areas of chemistry, especially in homogeneous and heterogeneous renewable energy catalysis. Such reactions may depend on explicit interactions with ions and solvent molecules that are nontrivial to characterize. Rigorously modeling explicit solvent effects with molecular dynamics usually brings steep computational costs while the performance of continuum solvent models such as polarizable continuum model (PCM), charge-asymmetric nonlocally determined local-electric (CANDLE), conductor-like screening model for real solvents (COSMO-RS), and effective screening medium method with the reference interaction site model (ESM-RISM) are less well understood for reaction mechanisms. Here, we revisit a fundamental aqueous hydride transfer reaction-carbon dioxide (CO2) reduction by sodium borohydride (NaBH4)-as a test case to evaluate how different solvent models perform in aqueous phase charge migrations that would be relevant to renewable energy catalysis mechanisms. For this system, quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations almost exactly reproduced energy profiles from QM simulations, and the Na+ counterion in the QM/MM simulations plays an insignificant role over ensemble averaged trajectories that describe the reaction pathway. However, solvent models used on static calculations gave much more variability in data depending on whether the system was modeled using explicit solvent shells and/or the counterion. We pinpoint this variability due to unphysical descriptions of charge-separated states in the gas phase (i.e., self-interaction errors), and we show that using more accurate hybrid functionals and/or explicit solvent shells lessens these errors. This work closes with recommended procedures for treating solvation in future computational efforts in studying renewable energy catalysis mechanisms.

Kinetic effects of molecular clustering and solvation by extended networks in zeolite acid catalysis

Abstract: Reactions catalyzed within porous inorganic and organic materials and at electrochemical interfaces commonly occur at high coverage and in condensed media, causing turnover rates to depend strongly on interfacial structure and composition, collectively referred to as “solvent effects”. Transition state theory treatments define how solvation phenomena enter kinetic rate expressions, and identify two distinct types of solvent effects that originate from molecular clustering and from the solvation of such clusters by extended solvent networks. We review examples from the recent literature that investigate reactions within microporous zeolite catalysts to illustrate these concepts, and provide a critical appraisal of open questions in the field where future research can aid in developing new chemistry and catalyst design principles.

Solvent Effects in Halogen and Hydrogen Bonding Mediated Electrochemical Anion Sensing in Aqueous Solution and at Interfaces

Abstract: Sensing anionic species in competitive aqueous media is a well-recognised challenge to long-term applications across a multitude of fields. Herein, we report a comprehensive investigation of the electrochemical anion sensing performance of novel halogen bonding (XB) and hydrogen bonding (HB) bis-ferrocene-(iodo)triazole receptors in solution and at self-assembled monolayers (SAMs), in a range of increasingly competitive aqueous organic solvent media (ACN/H2 O). In solution, the XB sensor notably outperforms the HB sensor, with substantial anion recognition induced cathodic voltammetric responses of the ferrocene/ferrocenium redox couple persisting even in highly competitive aqueous solvent media of 20 % water content. The response to halides, in particular, shows a markedly lower sensitivity to increasing water content associated with a unique halide selectivity at unprecedented levels of solvent polarity. The HB sensor, in contrast, generally displayed a preference towards oxoanions. A significant surface-enhancement effect was observed for both XB/HB receptive films in all solvent systems, whereby the HB sensor generally displayed larger responses towards oxoanions than its halogen bonding analogue.

A Novel M8L6 Cubic Cage that Binds Tetrapyridyl Porphyrins; Cage and Solvent Effects in Cobalt-porphyrin-catalyzed Cyclopropanation Reactions.

Abstract: Confinement of a catalyst can have a significant impact on catalytic performance and can lead to otherwise difficult to achieve catalyst properties. Herein, we report the design and synthesis of a novel caged catalyst system Co-G@Fe8 (Zn-L ⋅ 1)6 , which is soluble in both polar and apolar solvents without the necessity of any post-functionalization. This is a rare example of a metal-coordination cage able to bind catalytically active porphyrins that is soluble in solvents spanning a wide variety of polarity. This system was used to investigate the combined effects of the solvent and the cage on the catalytic performance in the cobalt catalyzed cyclopropanation of styrene, which involves radical intermediates. Kinetic studies show that DMF has a protective influence on the catalyst, slowing down deactivation of both [Co(TPP)] and Co-G@Fe8 (Zn-L ⋅ 1)6 , leading to higher TONs in this solvent. Moreover, DFT studies on the [Co(TPP)] catalyst show that the rate determining energy barrier of this radical-type transformation is not influenced by the coordination of DMF. As such, the increased TONs obtained experimentally stem from the stabilizing effect of DMF and are not due to an intrinsic higher activity caused by axial ligand binding to the cobalt center ([Co(TPP)(L)]). Remarkably, encapsulation of Co-G led to a three times more active catalyst than [Co(TPP)] (TOFini ) and a substantially increased TON compared to both [Co(TPP)] and free Co-G. The increased local concentration of the substrates in the hydrophobic cage compared to the bulk explains the observed higher catalytic activities.

Quantifying Interactions and Solvent Effects Using Molecular Balances and Model Complexes.

Abstract: ConspectusWhere the basic units of molecular chemistry are the bonds within molecules, supramolecular chemistry is based on the interactions that occur between molecules. Understanding the “how” an...

Solvent Effects on Fluorescence Properties of Carbon Dots: Implications for Multicolor Imaging.

Abstract: Carbon dots (CDs) are synthesized by the solvothermal method with four kinds of solvents including water, dimethylformamide (DMF), ethanol, and acetic acid (AA). The aqueous solutions of the above CDs emit multiple colors of blue (470 nm), green (500 nm), yellow (539 nm), and orange (595 nm). The structures, sizes, and chemical composition of the CDs are characterized by transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The optical properties of multicolored CDs are analyzed by UV-vis absorption and photoluminescence (PL) spectra. It has been revealed that DMF is the key solvent to synthesized CDs for the red shift of fluorescence emission, which could be enhanced by adding an AA solvent. The structures of functional groups such as the contents of graphitic N in carbon cores and oxygen-containing functional groups on the surface of CDs are affected by these four solvents. According to the oxidation and selective reduction of NaBH4, the implication for multicolor imaging has been discussed based on the COOH, C-O-C, and C=O functional groups.

Solvent Effects on Ultrafast Photochemical Pathways.

Abstract: ConspectusPhotochemical reactions are increasingly being used for chemical and materials synthesis, for example, in photoredox catalysis, and generally involve photoexcitation of molecular chromophores dissolved in a liquid solvent. The choice of solvent influences the outcomes of the photochemistry because solute-solvent interactions modify the energies of and crossings between electronic states of the chromophores, and they affect the evolving structures of the photoexcited molecules. Ultrafast laser spectroscopy methods with femtosecond to picosecond time resolution can resolve the dynamics of these photoexcited molecules as they undergo structural and electronic changes, relax back to the ground state, dissipate their excess internal energy to the surrounding solvent, or undergo photochemical reactions. In this Account, we illustrate how experimental studies using ultrafast lasers can reveal the influences that different solvents or cosolutes exert on the photoinduced nonadiabatic dynamics of internal conversion and intersystem crossing in nonradiative relaxation pathways. Although the environment surrounding a solute molecule is rapidly changing, with fluctuations in the coordination to neighboring solvent molecules occurring on femtosecond or picosecond time scales, we show that it is possible to photoexcite selectively only those molecular chromophores transiently experiencing specific solute-solvent interactions such as intermolecular hydrogen bonding.The effects of different solvation environments on the photodynamics are illustrated using four selected examples of photochemical processes in which the solvent has a marked effect on the outcomes. We first consider two aromatic carbonyl compounds, benzophenone and acetophenone, which are known to undergo fast intersystem crossing to populate the first excited triplet state on time scales of a few picoseconds. We show that the nonadiabatic excited-state dynamics are modified by transient hydrogen bonding of the carbonyl group to a protic solvent or by coordination to a metal cation cosolute. We then examine how different solvents modify the competition between two alternative relaxation pathways in a photoexcited UVA-sunscreen molecule, diethylamino hydroxybenzoyl hexyl benzoate (DHHB). This relaxation back to the ground electronic state is an essential part of the effective operation of the sunscreen compound, but the dynamics are sensitive to the surrounding environment. Finally, we consider how solvents of different polarity affect the energies and lifetimes of excited states with locally excited or charge-transfer character in heterocyclic organic compounds used as excited-state electron donors for photoredox catalysis. With these and other examples, we seek to develop a molecular level understanding of how the choice of solution environment might be used to control the outcomes of photochemical reactions.