Reaction Solvent Research Articles

Strengthen Water O−H Bond in Electrolytes for Enhanced Reversibility and Safety in Aqueous Aluminum Ion Batteries

AbstractAqueous aluminum‐ion batteries present a promising prospect for large‐scale energy storage applications, owing to the abundance, inherent safety, and the high theoretical capacity of aluminum. However, their voltage output and energy density are significantly hindered by challenges such as complex hydrogen evolution and uncontrollable solvation reactions. In this work, we demonstrate that water decomposition is restrain by increasing the electron density of water protons and increasing the dissociation energy of H2O through robust dipole interactions with highly polar dimethylformamide (DMF) molecules. Moreover, the incorporation of dimethyl methylphosphonate (DMMP) flame retardant effectively addresses the flammability risk arising from a substantial presence of organic additives The in‐depth study with experimental and theoretical simulations reveals that the water‐poor solvation structure with reduced water activity is achieved, which can (i) effectively mitigate undesired solvated H2O‐mediated side reactions on the Al anode; (ii) boost the de‐solvation kinetics of Al3+ while preventing cathode structural distortion; (iii) reduce the flammability of hybrid electrolytes. As a proof of concept, the Al//AlxMnO2 full cell employing a hybrid electrolyte demonstrate enhanced stability (deliver 335 mAh g−1 while retaining 71 % capacity for 400 cycles) compared to those with pure electrolyte.

Solvent-free catalytic synthesis of ureas from amines and carbon dioxide under atmospheric pressure using oxovanadium(V) catalyst with silylating reagent

Abstract Efficient utilization of carbon dioxide for the synthesis of valuable compounds is considered to be essential for the future sustainable society. Herein, N,O-bis(trimethylsilyl)acetamide (BSA), which acts not only as a silylating reagent but also as a reaction solvent, was demonstrated to facilitate the solvent-free catalytic synthesis of ureas in one-step from amines and carbon dioxide under atmospheric pressure using a commercially available air-stable NH4VO3 catalyst. This catalytic system was applicable to a wide range of substrate and a gram-scale reaction. One-step preferential synthesis of unsymmetrical ureas was also realized.

Ambient Pressure Hydroformylation – A Key Step to Meso‐Alkyl BODIPYs

AbstractHerein, a highly efficient five‐step reaction sequence to meso‐alkyl BODIPYs is presented. In our previous work, the hydroformylation of terminal alkenes was used to generate an aldehyde from an alkene via rhodium catalysis and use them in a subsequent tandem reaction to obtain BODIPY dyes. However, the use of higher pressures and therefore autoclaves as well as their necessary equipment might limit others to use this method. The refined approach in this work employs ambient pressure hydroformylation, done in a simple Schlenk tube and using a CO/H2 balloon, as key step towards an easier meso‐alkyl BODIPY synthesis. Additionally, the use of MTBE instead of chloroform as reaction solvent results in a greener approach. Readily available and easily synthesizable alkenes as well as different pyrrole building blocks can be used to extend the range of known alkyl‐BODIPYs. The synthesis of 23 derivatives with overall yields of up to 67 % demonstrates the wide applicability and advantages of the refined method.

Neoteric solvents for metal catalysed coupling reactions

Catalysis is a green methodology aimed at optimizing synthetic procedures, because it simplifies the design of target molecules and reduces energy and material use. Catalytic reactions often rely on polar aprotic solvents, such as dimethylformamide (DMF) or acetonitrile, which present environmental and health issues. In response, manufacturers and researchers are exploring greener alternatives derived from residual biomass, that reduce the negative environmental impact of traditional solvents. These new classes of solvents are termed ‘neoteric’ to distinguish them from traditional solvents with well-established use. This review highlights key findings on the use of these new solvents in metal catalysed coupling reactions.

Electric Field-Induced Sequential Prototropic Tautomerism in Enzyme-like Nanopocket Created by Single Molecular Break Junction.

Mastering the control of external stimuli-induced chemical transformations with detailed insights into the mechanistic pathway is the key for developing efficient synthetic strategies and designing functional molecular systems. Enzymes, the most potent biological catalysts, efficiently utilize their built-in electric field to catalyze and control complex chemical reactions within the active site. Herein, we have demonstrated the interfacial electric field-induced prototropic tautomerization reaction in acylhydrazone entities by creating an enzymatic-like nanopocket within the atomically sharp gold electrodes using a mechanically controlled break junction (MCBJ) technique. In addition to that, the molecular system used here contains two coupled acylhydrazone reaction centers, hence demonstrating a cooperative stepwise electric field-induced reaction realized at the single molecular level. Furthermore, the mechanistic studies revealed a proton relay-assisted tautomerization showing the importance of external factors such as solvent in such electric field-driven reactions. Finally, single-molecule charge transport and energetics calculations of different molecular species at various applied electric fields using a polarizable continuum solvent model confirm and support our experimental findings. Thus, this study demonstrates that mimicking an enzymatic pocket using a single molecular junction's interfacial electric field as a trigger for chemical reactions can open new avenues to the field of synthetic chemistry.

Multipoint Anionic Bridge: Asymmetric Solvation Structure Improves the Stability of Lithium-Ion Batteries.

In this study, a novel concept of multipoint anionic bridge (MAB) is proposed and proved, which utilizes anions with different sites to connect with the asymmetric solvation structure (ASS). Compared to usual solvation structures, this study utilizes the multifunctional groups of difluoro(oxalate)borate anion (ODFB-), which can connect with Li+. By tailoring the concentration, the anion serves as a bridge between different solvated structures. The electrolyte is investigated through in situ techniques and simulations to draw correlations between different solvation structures and reaction pathways. The proposed design demonstrates remarkable high-temperature performance on both the anode and cathode sides, enabling stable cycling of LCO||graphite (0.5 Ah, 1.0 C) pouch cell for over 200 cycles at 80°C and facilitating Li||MCMB and Li||LFP cells to deliver stable performance for 200 cycles at 100°C. This work paves the way for the development of high-performance electrolyte systems by designing and using new multipoint anions to construct ASSs.

Computational investigation of water as catalyst and solvent in aromatic nucleophilic substitution reaction of 2-bromopyridine

Computational investigation of water as catalyst and solvent in aromatic nucleophilic substitution reaction of 2-bromopyridine

Chiral Metal Self-assemblies of Zirconium-Tetrahedra and Their Second Harmonic Generation Activity.

The chirality of metal-organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units for the construction of noncentrosymmetric materials. Herein, by self-assembling the 4,4',4''-nitrilotribenzoic acid (H3NBA) with bis(cyclopentadienyl)-zirconium dichloride (Cp2ZrCl2, Cp = η5-C5H5) in different solvent conditions, we have obtained three hierarchical packing modes of metallo-tetrahedra with distinct spatial symmetry groups (designated as Zr-α, Zr-β, and Zr-γ). Among them, Zr-α employs a simple cubic arrangement and is a common centrosymmetric superstructure, which consists of a pair of equimolar metallo-tetrahedra enantiomers in its unit cell. While Zr-β results in conglomerates with spontaneous resolution without using any resolving agents, giving rise to two enantiopure entities separately (Zr-β-P, Zr-β-M). More importantly, Zr-γ breaks the inversion center of symmetry and crystallizes into a racemic yet non-centrosymmetric superstructure with face-centered cubic packing mode. Based on the non-centrosymmetric nature, the hierarchical superstructure Zr-γ displayed good second harmonic generation activities. This work presents a successful instance wherein the reaction solvent induces the modulation of intermolecular packing mode to afford non-centrosymmetric solid materials, which can greatly promote the development of noncentrosymmetric solid (NCS) materials.

Furfural production from xylan using a Pueraria Residues carbon-based solid-acid catalyst.

The conversion of biomass into high value-added platform compounds is an important method of biomass utilization. The conversion of hemicellulose represented by xylan into furfural can not only reduce the consumption of fossil fuels, but also promotes the development and utilization of non-edible biomass resources. In this study, a bifunctional solid-acid catalyst prepared from agricultural and forestry waste Pueraria (P. eduli) Residues was used to convert xylan into furfural in a biphasic system. In this study, P. eduli Residues was used as raw material to prepare a P. eduli Residues-based carbon solid-acid catalyst (PR/C-SO3H-Fe) by one-step sulfonation carbonization and impregnation. The catalyst catalyzes the conversion of xylan to furfural in a biphasic system (2-methyltetrahydrofuran/water). The physicochemical properties of the catalysts were characterized by X-ray powder diffraction, scanning electron microscopy, differential thermogravimetric analysis, Brunauer-Emmett-Teller surface area, Fourier transform infrared spectroscopy and ammonia temperature-programmed desorption. Subsequently, the experimental conditions were studied and optimized, such as metal species, iron ion concentration, reaction time and temperature, volume ratio of organic phase to water phase and ratio of substrate to catalyst. The results showed that under conditions of 160 °C, 50 mg catalyst, 100 mg xylan and 7 mL reaction solvent, the yield of furfural could reach 78.94% after 3 h of reaction. This study provides an effective research method for the conversion of xylan into furfural, and provides a reference for the catalytic conversion and utilization of hemicellulose in agricultural and forestry biomass. It also provides a feasible method for the resource utilization of agricultural and forestry waste. © 2024 Society of Chemical Industry.

Tandem Synthesis of Piriqualone and Analogues Using Deep Eutectic Solvents: Photophysical and Theoretical Insights

This study presents a sustainable chemical approach for the tandem synthesis of Piriqualone a sedative and anxiolytic drug and its analogues using a green protocol. The research investigates the ability of deep eutectic solvents (DESs) to act as catalysts as well as solvent in a tandem reaction involving metal‐free dehydrogenation and sp3 C‐H bond functionalization, leading to the formation of styryl‐heterocyclic compounds (7a‐p). These styryl derivatives were thoroughly characterized through spectral analysis and photophysical property evaluation. The relationship between chemical structure and AIE properties was particularly examined for compound 7n. Additionally, the experimental findings were corroborated by density functional theory (DFT) calculations. The structures of compounds 7j, 7p and 7fa were further validated through single crystal X‐ray diffraction (XRD) analysis.

Rod‐Like Microcrystal Scintillators Based on Organic–Inorganic Hybrid Copper Halides for X‐Ray Imaging

AbstractCopper‐based organic–inorganic hybrid halides (OIHHs) have garnered significant interest in X‐ray imaging due to their flexible structural adjustability, efficient light emission, strong X‐ray absorption, etc. Herein, four copper‐based OIHH crystals composed of the same organic ligands (isopropyl triphenylphosphonium cations, IPP+) and inorganic parts (Cu2I42−) are synthesized by varying the ratios of raw materials and types of reaction solvents. Although these crystals share identical structures, they exhibit different luminescent behaviors (blue, green, white, and yellow) attributed to vacancy defects originating from CuI. Notably, the novel copper‐based OIHH (CP2) with green emission shows the best luminescence efficiency (99.54%) and excellent scintillation performance (50675 photons MeV−1). The traditional technology of scintillation screens mixing scintillator powders and polymers often results in light scattering due to powder aggregation and inhomogeneity. To address this challenge, the dispersant polyvinyl pyrrolidone is introduced to prepare uniform rod‐like microcrystals of CP2. The scintillation screen based on CP2 microcrystals achieves a high spatial resolution of 16–18 lp mm−1, surpassing the resolution of most copper‐based OIHH scintillators. Furthermore, it is imaging capabilities are validated using a commercial X‐ray flat panel detector, demonstrating imaging performance comparable to that of commercial scintillators.

Gold(III) Catalysis in Ionic Liquids: The Case Study of Coumarin Synthesis

AbstractWell‐defined (P,C)‐cyclometalated Au(III) complexes proved to be able to catalyze the synthesis of coumarins by intramolecular hydroarylation of a broad range of aryl propiolates under mild and practical conditions (0.1–2 mol% catalyst, 25–40 °C, 1–24 hours). The use of an ionic liquid as reaction solvent allowed to drastically decrease the amount of Brönsted acid used to unlock the catalyst regeneration step. The effect of the nature of the acid additive and of the ionic liquid anion have been assessed. Preliminary results on the extension of this methodology to the cyclization of aryl propargyl ethers are also presented.

High-Coverage Disulfide Mapping Enabled by Programmable Disulfide-Ene Reaction Integrated onto a Bottom-Up Protein Analysis Workflow.

Mapping disulfide linkages is crucial for characterizing pharmaceutical proteins during drug development and quality control. Traditional bottom-up protein analysis workflows often suffer from incomplete mapping for tryptic peptides consisting of multiple disulfide bonds. Although the employment of a partial reduction of disulfide bonds can improve disulfide mapping, it becomes a bottleneck of analysis because individual tuning is often needed. Herein, we have developed an online disulfide-ene reaction system in which the composition of the reaction solvent can be programmed to achieve optimal partial reduction of tryptic disulfide peptides after liquid chromatography separation. By coupling this system onto a bottom-up protein analysis workflow, high coverage for sequencing (71-83%) and disulfide mapping (84-100%) was achieved for standard proteins consisting of 4-19 disulfide bonds. The analytical capability was further demonstrated by mapping 13 scrambled disulfide bonds in lysozyme and achieving compositional analysis of IgG isotypes (κ and λ) and subclasses (IgG1-IgG4) from human plasma.

Strengthen Water O-H Bond in Electrolytes for Enhanced Reversibility and Safety in Aqueous Aluminum Ion Batteries.

Aqueous aluminum-ion batteries present a promising prospect for large-scale energy storage applications, owing to the abundance, inherent safety, and the high theoretical capacity of aluminum. However, their voltage output and energy density are significantly hindered by challenges such as complex hydrogen evolution and uncontrollable solvation reactions. In this work, we demonstrate that water decomposition is restrain by increasing the electron density of water protons and increasing the dissociation energy of H2O through robust dipole interactions with highly polar dimethylformamide (DMF) molecules. Moreover, the incorporation of dimethyl methylphosphonate (DMMP) flame retardant effectively addresses the flammability risk arising from a substantial presence of organic additives The in-depth study with experimental and theoretical simulations reveals that the water-poor solvation structure with reduced water activity is achieved, which can (i) effectively mitigate undesired solvated H2O-mediated side reactions on the Al anode; (ii) boost the de-solvation kinetics of Al3+ while preventing cathode structural distortion; (iii) reduce the flammability of hybrid electrolytes. As a proof of concept, the Al//AlxMnO2 full cell employing a hybrid electrolyte demonstrate enhanced stability (deliver 335 mAh g-1 while retaining 71% capacity for 400 cycles) compared to those with pure electrolyte.

Understanding Selectivity in Product Distributions from Laser Ablation of Organic Liquids.

Pulsed laser ablation in organic solvents is widely used to produce oxide-free metal and metal carbide nanoparticles, often with carbon coatings resulting from laser-induced reactions in the organic solvent. To gain insight into how the molecular structure of the solvent affects these reaction pathways, this work investigates ablation of the C6H14 isomers n-hexane, 2-methylpentane, and 3-methylpentane through characterization of the gas and liquid products with mass spectrometry. Ablation of each C6H14 isomer produces a distinct distribution of product molecular weights and isomers. 2-methylpentane preferentially produces C3 and C9, whereas 3-methylpentane produces C2, C4, C8, and C10 products. These preferential product distributions, along with the lack of such selectivity in n-hexane, arise from differences in the most favorable C-C bond scission pathways in each C6H14 isomer. Moreover, the particular isomers of C8H18, C9H20, C10H22, and C12H26 produced by ablation of each C6H14 isomer indicate that the vast majority of reaction pathways involve addition reactions between a fragment radical and parent C6H14 or between two C6H14 molecules, without molecular rearrangement. This propensity toward direct addition suggests that the chemical reactions induced by ultrashort pulsed laser ablation proceed on faster time scales than those of radical rearrangements.

Quantitative Reactivity Models for Oxidative Addition to L2Pd(0): Additional Substrate Classes, Solvents, and Mechanistic Insights.

Quantitative molecular structure-reactivity models are useful for generating predictions to guide synthesis design, and in formulating and testing mechanistic hypotheses. We report an expanded multivariate linear regression (MLR) model for the rate of (hetero)aryl (pseudo)halide oxidative addition to L2Pd(0), here exemplified by Pd(PCy3)2. This builds on a prior model from our group, with additional substrate classes (aryl chlorides and iodides) and reaction solvents (THF, toluene, THF/DMF mixture). Overall solvent effects across the entire substrate set are minimal under these conditions, enabling a unified MLR model without introduction of new molecular descriptors beyond the original five. Examining the mechanistic origin of the two molecular electrostatic potential (ESP) descriptors led to generation of a simpler, four descriptor model that is suitable for aryl halides, but not for 2-halopyridines. Using this model we identified a mechanistic outlier, 2-pyridyl triflate, which undergoes a nucleophilic displacement oxidative addition that does not involve the adjacent nitrogen atom. Finally, we discuss the relationship between C-X bond strength and oxidative addition rates, and compare the intrinsic bond strength index (IBSI) to bond dissociation enthalpy (BDE) as a bond strength descriptor.

Selective hydrogenation of 5‐hydroxymethylfurfural to 5‐hydroxymethyltetrahydrofurfural over heterogeneous Pd catalyst under mild conditions

5‐Hydroxymethylfurfural (5‐HMF) derived from lignocellulose represents an important platform molecule that could be employed in the selective hydrogenation of the furan ring to prepare 5‑hydroxymethyltetrahydrofurfural (HMTHF). However, the reported catalytic systems for the synthesis of HMTHF using 5‐HMF still require additional hydrogen pressure. In this study, the Pd/ZrO2 catalyst with uniformly dispersed Pd nanoparticles was prepared via a simple impregnation reduction process. This catalyst exhibited excellent catalytic activity and selectivity for the hydrogenation of 5‐HMF to HMTHF. High HMTHF yield up to 92.3% was produced under mild reaction conditions of ambient hydrogen pressure and room temperature in methanol solvent. This result was superior to the most catalytic systems that had been reported so far. The mechanism study revealed that the active hydrogen species on the surface of the Pd nanoparticles and the reaction solvent in this study were the pivotal factors influencing the hydrogenation of furan rings in 5‐HMF.

Amine Exchange of Aminoalkylated Phenols as Dynamic Reaction in Benzoxazine/Amine-Based Vitrimers.

Bisfunctional benzoxazine and polyether diamine-based polymers show Arrhenius-like stress-relaxation varying with stoichiometry and polymerization temperatures proving vitrimeric behavior. Molecular structural investigations reveal the presence of different aminoalkylated phenols occurring at varying ratios depending on polymer composition and polymerization conditions. The vitrimeric mechanism is found to involve an amine exchange reaction of aminoalkylated phenols in an equilibrium reaction like a nucleophilic substitution reaction. As determined by molecular studies and dissolution experiments in reactive solvents, aliphatic and aromatic primary as well as aliphatic secondary amines in the polybenzoxazine structure can act as nucleophiles in reaction with electrophilic methylene bridges. Thus, aminoalkylated phenols proved to be a relevant structural motif resulting in a vitrimeric polybenzoxazine due to amine exchange reaction.

Enzymatic synthesis of aromatic biobased polymers in green, low-boiling solvents

Given the urge to accelerate the substitution of petrol-derived solvents not only in more traditional fields like pharmaceuticals, personal care, or electronics but also in innovative research processes, this work focuses on the utilisation of four biobased solvents as media for the enzymatic synthesis of aliphatic-aromatic polyesters. As building blocks, the lignin-derived diethyl-2,4-pyridinedicarboxylate was selected as the potentially biobased, aromatic component while more classical diols such as 1,4-butanediol and 1,8-octanediol were used as the aliphatic portion. Results show that among the tested green solvents (cyclohexanone, phenetole, anisole and eucalyptol), the most suitable medium for lipase B from Candida antarctica-catalysed polycondensation reactions was eucalyptol that allowed reach monomer conversions >95 % and number average molecular weights up to 3500 g·mol−1. On the other hand, cyclohexanone led to the lowest monomer conversions (<80 %) and molecular weights (Mn<500 g·mol−1) confirming once again the unsuitability of ketone-containing solvents for enzymatic esterification and transesterification reactions. The lipase could be used up to three times, in eucalyptol as a solvent, without a significant decrease in monomer conversion or molecular weight.

Controlling Chemoselectivity in Ruthenium(II)-Induced Cyclization of Aniline-Functionalized Alkynes.

The cyclization of heteroatom-functionalized alkynes induced by d6-transition-metal centers has traditionally been associated with the vinylidene pathway. However, recent evidence suggests that d6-transition-metal centers can also activate alkynes through non-vinylidene pathways. In this study, we conducted a comprehensive experimental and theoretical investigation into the reactions between the Ru(II) complex [Ru([9]aneS3)(bpy)(OH2)]2+ and 2-alkynylanilines. Our study revealed that the selectivity between the vinylidene and non-vinylidene pathways can be tuned by reaction temperature, substrate, and solvent polarity. This strategic control allows for the preferential formation of either C2- or C3-metalated indole zwitterion complexes. Additionally, we identified a rare decyclization mechanism that enables the conversion of C2-metalated indoles to C3-metalated indoles, underscoring the significance of product stability in these pathways. Overall, this work demonstrates practical approaches to control the preference between vinylidene and non-vinylidene pathways, which is crucial for the design of new catalysts and metalated heterocyclic complexes.