Onium Research Articles

"Cation Pool" generated from DMSO and 1,2-dihaloethanes and their application in organic synthesis.

Conventionally, carbenium and onium ions are prepared in the presence of nucleophiles due to their instability and transient nature. The nucleophiles that are unstable or inert to the reaction media cannot be used for reaction with the cationic species to access the desired compounds. To overcome these limitations, developing methods for generating organic cations irreversibly in the absence of nucleophiles is essential. The "cation pool" method developed by Yoshida and co-workers stands out as a reliable strategy to generate and accumulate the reactive cations in solution in the absence of nucleophiles. The cation pool method involves the electrolysis of the substrate in the absence of nucleophiles, usually at low temperature. Moreover, the generation of halogen and chalcogen cations through electrolysis needs extra care because of their low stability. This review covers our effort in generating and accumulating halogen cations as "cation pools", most importantly by simply heating a mixture of dimethyl sulfoxide (DMSO) and 1,2-dihaloethane (DXE, X = Cl, Br, I), and their use in the halogenation reactions. Furthermore, condition-dependent Pummerer-type fragmentations of DMSO-stabilized halogen cations to methyl(methylene)sulfonium ions and chlorodimethylsulfonium ions for synthetic applications are described.

Mechanistic investigation of methanol-to-olefins conversion catalyzed by H-ZSM-5 zeolite: a DFT study.

The mechanisms for the formation of the first C - C bond and lower olefins on methanol to olefins (MTO) conversion on H-ZSM-5 had been focused in dispute. In this paper, density functional theory has been used to study the reaction mechanisms of methanol to olefins on ZSM-5. The configurations of reactants, intermediates, products and transition state of the numerous reactions involved in such a process have been optimized, as well as the elementary reactions related to these configurations were determined by the calculation of corresponding activation energy barriers and reaction heats. Here, two different kinds of the mechanisms were proposed for the formation of dimethylether (DME), one involving an associative interaction of two methanol molecules with the zeolite Brønsted acid sites and the other occurring via a surface methoxy species and a methanol molecule. A critical intermediate of the methoxy methyl cation was theoretically verified by the reaction of the methoxy species and dimethylether. Besides, it was found that the first intermediates containing a C - C bond were 1,2-dimethoxyethane and 2-methoxy-ethanolare, in which the former was formed from methoxy species with dimethyl ether and the latter was formed from methanol by onium ions((CH3)2O+CH2CH2OCH3), respectively. For the whole reaction mechanism, the results in this paper indicated that the ethene formation is more favorable than propylene formation due to the low activation energy barrier for ethene formation (123.49 vs. 162.09kJ.mol-1). From these calculations, it would be concluded that ethene is the first alkene product that induces the occurrence of the hydrocarbon pool mechanism. All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave (PAW) method. PBE-D3 was used in the whole DFT calculations and CI-NEB was used to locate transition state.

Organometallic Ionic Plastic Crystals Incorporating Cationic Half-Sandwich Complexes.

Ionic plastic crystals (IPCs), characterized by nearly spherical molecular ions, exhibit remarkable solid-state characteristics including high ionic conductivity. However, most IPCs are organic onium salts. Incorporating organometallic half-sandwich complexes into IPCs is challenging owing to their low-symmetry structures. This paper introduces a novel series of IPCs composed of salts derived from half-sandwich organometallic complexes. We synthesized five salts of [Ru(Cp)(tmeda)(CO)]X (tmeda = N,N,N',N'-tetramethyl-1,2-ethanediamine, X = anion) with different anions and examined their phase behavior, crystal structures, and molecular motion in the solid-state. Salts featuring the CPFSA (= 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide), B(CN)4-, and FSA- (= (FSO2)2N-) anions underwent phase transitions to an IPC phase with a CsCl-type structure in the temperature range of 327-364 K. Employing smaller anions led to an increase in the transition temperature. In each salt, the coordination number, representing the number of anions surrounding one cation, remained eight in IPC and low-temperature phases. However, salts containing smaller anions (CF3BF3- and PF6-) displayed a rotator phase rather than the IPC phase. In these cases, the coordination numbers were six at low temperatures.

Low molar mass polycarbonate diols from degradation of terpolymers obtained by epoxide/o-phthalaldehyde/CO2 copolymerization

In this manuscript, we describe the synthesis of low molar mass polycarbonate diols by acid cleavage of labile acetal linkages included in high molar mass poly(ether-co-carbonate-co-acetal) terpolymers. These copolymers were prepared by terpolymerization of propylene oxide (PO) with o-phthalaldehyde (OPA) and carbon dioxide (CO2), using triethyl borane (TEB) as activator and an onium salt as initiator. The advantage of this strategy of synthesis of poly(propylene carbonate) diols (PPC-diols) lies in the minute amounts of TEB and initiator required. Moreover, OPA could be isolated through post-hydrolysis of the terpolymers and recycled for subsequent use. We also demonstrated that this strategy works for the synthesis of low molar mass poly(ethylene carbonate) diols (PEC-diols). The structural integrity of the terpolymers before and after acid treatment, the characterization of low molar mass PPC-diols, and recycling process of OPA were carried out by 1H NMR spectroscopy, gel permeation chromatography, and matrix-assisted laser desorption ionization time of flight (MALDI-TOF) MS.

Two- and three-photon processes during photopolymerization in 3D laser printing.

The performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to an efficient and frequently used class of photoinitiators in 3D laser printing, and explain the molecular bases of FRP initiation upon DETC photoactivation. Depending on the presence of a co-initiator, DETC causes radical generation either upon two-photon- or three-photon excitation, but the mechanism for these processes is not well understood so far. Here, we show that the unique three-photon based radical formation by DETC, in the absence of a co-initiator, results from its excitation to highly excited triplet states. They allow a hydrogen-atom transfer reaction from the pentaerythritol triacrylate (PETA) monomer to DETC, enabling the formation of the reactive PETA alkyl radical, which initiates FRP. The formation of active DETC radicals is demonstrated to be less spontaneous. In contrast, photoinitiation in the presence of an onium salt co-initiator proceeds via intermolecular electron transfer after the photosensitization of the photoinitiator to the lowest triplet excited state. Our quantum mechanical calculations demonstrate photophysical processes upon the multiphoton activation of DETC and explain different reactions for the radical formation upon DETC photoactivation. This investigation for the first time describes possible pathways of FRP initiation in 3D laser nanoprinting and permits further rational design of efficient photoinitiators to increase the speed and sensitivity of 3D laser nanoprinting.

Facile synthesis of polycarbonates from biomass-based eugenol: catalyst optimization for selective copolymerization of CO2 and eugenol to achieve polycarbonates

A series of Co(iii) and Cr(iii)(salen) complexes in the presence of onium salts have been examined for the coupling of CO2 and biomass based eugenol epoxide for the selective production of polycarbonates in a partially sustainable process.

A bottom-up puzzle strategy for P/B co-doped carbon nanosheets as efficient oxygen reaction electrocatalysts

Preparing metal-free and non-N-doped carbon-based electrocatalysts via pyrolysis encounters a significant challenge of low controllability for microstructure modulation and limited electrocatalytic activity. Herein, a bottom-up puzzle strategy is proposed to fabricate a series of phosphorus and boron co-doped carbon (P-BC) nanosheets. These P-BC nanosheets manifest diverse morphologies and distinct heteroatom doping levels, achieved through the innovative utilization of four similar P onium salts featuring varying benzene ring arrangements, coupled with a fixed B onium salt. Among them, the flat 4P-BC nanosheets with abundant P/B heteroatoms exhibit the optimal oxygen reduction reaction (ORR) performance (E1/2 = 0.79 V, jL = 5.77 mA cm−2), and the assembled zinc-air battery displays a large power density (163 mW cm−2) and excellent long-term durability (450 cycles), which is attributed to the high specific surface area, enhanced defects or disorder, and ample P/B-doping induced active sites for electrochemical reaction. The assembly mechanism of functional units in solution and their intricate evolution at high temperature are elucidated for various P-BC nanosheets. This work elaborates the influence of precursors functional units on the resulting microstructure attributes and active sites properties, providing a novel avenue for the rational design and optimization of metal-free and heteroatom-doped carbon electrocatalysts.

A flavonoid salt probe for distinguishing between tumor and normal cells

YH-2 represents an innovative, non-invasive fluorescent probe featuring a structure based on flavonoid onium salts. It is characterized by a well-suited Stokes shift and emits in the near-infrared (NIR) wavelength range. Its capacity to distinguish between HeLa cells, HepG2 cells, and LO2 cells is attributed to differential intracellular viscosity. Experimental results validate the heightened viscosity of organelles, such as the endoplasmic reticulum (ER), mitochondria and lysosomes in tumor cells compared to LO2 cells. Of paramount importance, YH-2 demonstrates the capability to swiftly image tumors within a mere 20 min following tail vein injection and this imaging ability can be sustained for an extended period of up to 5 h. This method offers a potential tumor diagnostic strategy in vivo.

Construction of a mitochondria-targeted near-infrared fluorescence turn-on fluorescent probe for H2S detection and imaging in living cells and drug-induced mice inflammatory models

The mechanism of the interaction between the signaling molecule hydrogen sulfide (H2S) and mitochondria and its related diseases is difficult to elusive. Thus it is urgent to develop effective methods and tools to visualize H2S in mitochondria and in vivo. In this work, a robust mitochondrial-targeting NIR fluorescence “turn-on” fluorescent probe, NIR1, was reported, by adopting a Changsha-OH near-infrared (NIR) dye as the NIR fluorophore, a 2,4-dinitrophenyl (DNB) moiety as both the responsive site of the H2S and the fluorescence quenching group of the NIR fluorophore, and an oxygen onium ion site as the mitochondria-targeting group, for the detection and analysis of H2S in living Raw 264.7 cells and drug-induced inflammatory mice models. NIR1 exhibited a much smaller background fluorescence signal in lack of H2S, whereas strong enhanced NIR fluorescence “turn-on” was detected in the presence of H2S, these results showed a low detection limit (30.2 nM) for quantitative detection of H2S in aqueous solutions with concentrations ranging from 0 to 1 μM H2S. These characteristics were beneficial to direct detection and imaging analysis of H2S in complicated biosystems. Therefore, first, NIR1 was applied for the NIR detection of mitochondrial H2S in living inflammatory cells with satisfactory results. Finally, NIR1 was applied to detect H2S in drug-induced inflammatory mice models with agreeable results, demonstrating that NIR1 as a molecular tool has an excellent practical application in the study of the interaction between inflammatory and H2S.

Intra- and Intermolecular Cation-π Interactions between Onium Salts and Alkynes/Acetylene: Experimental and Theoretical Insights.

Cation-π interactions between various onium salts, alkynes, and acetylene were studied, taking into account the substituents of the triple bond, the nature of the anions, and the polarity of the solvent, through a combination of MP2 calculations and experiments. In an intramolecular setting, these data (including single-crystal X-ray crystallography) concurred with the stability of folded conformers of alkynyl onium salts, even substituted with electron-withdrawing groups. To examine the contribution of these interactions on the alkyne electronic population, a thorough in silico study was carried out using natural bonding orbital analysis of the conformers. Intramolecular interactions from sulfonium salt tethered to phenylalkyne were highlighted, as illustrated above by the computed folded conformation (MP2) along with noncovalent interaction (NCI) analysis. Furthermore, investigations of intermolecular interactions, involving acetylene or phenylacetylene with various onium ions, revealed the high energy interactions of their complexes with phenyldimethylsulfonium chloride, as illustrated above with the complex PhC≡CH/PhMe2SCl (MP2 calculations and NCI analysis).

Thermally initiated cationic frontal polymerization of epoxies and vinyl ethers through a lone onium salt

AbstractFrontal polymerization (FP) of epoxy monomers is typically achieved with a radical‐induced cationic frontal polymerization (RICFP) process that combines a thermal radical initiator with an onium salt superacid generator. In this paper, we show that both thermal and UV‐initiated cationic frontal polymerizations are possible for common epoxy and vinyl ether monomers with only an iodonium superacid generator in the absence of a standalone thermal radical initiator. Increasing superacid generator concentration resulted in an increase in front velocity, as did the addition of vinyl ether to epoxies. The front velocity is reduced by the addition of 4‐methoxyphenol (MeHQ), indicating free‐radicals play a significant role.

A latened catalytic strategy for low cure thermoset powder coating by post-dry-blending technique

Conventional thermoset powder coatings typically require curing at a high temperature of 190 °C for a minimum duration of 15 min, which poses challenges when applying them to heat-sensitive substrates and results in elevated energy costs. A solution known as low-temperature-curing powder coating (LCPC) has been developed to address this issue. By normally incorporating the curing catalyst into the coating system via hot extrusion, LCPC can achieve either a reduced curing temperature or a shortened curing period. However, the current extrusion method used for catalyst incorporation leads to undesirable side effects, such as compromised surface quality, shorter shelf-life and a narrower operational window for the hot-extrusion process involved in producing powder coatings. To overcome these challenges, a new strategy is proposed in this study, in which the tailor-made nano-catalyst is post-dry-blended into the powder coating instead of subjecting it to hot treatment with coating ingredients. This dry-blending catalyst (DBC), encapsulating nanosized fumed silica with catalysts by impregnation method, is introduced to the powder coating system before spraying, eliminating the need for hot-kneading into the powder coating system at the beginning. The DBC is attached to the surface of the particle realizing the interparticle contact mode and latening the catalysis. The dry-blended low-temperature-curing powder coating (DB-LCPC), containing a 0.03 % dosage of onium salt and 0.035 % of 2-methylimidazole, is identified as the optimum formulation due to its excellent surface quality, prominent chemical and mechanical characteristics. The sample successfully achieved low-temperature curing or a shortened curing time while maintaining excellent mechanical properties and chemical resistance. Furthermore, it exhibited superior coating appearances and a longer shelf-life compared to the hot-extruded sample. This novel DBC method has the potential to greatly enhance the adoption of low-temperature-curing powder coatings.

Asymmetric tandem conjugate addition and reaction with carbocations on acylimidazole Michael acceptors.

We present here a stereoselective tandem reaction based on the asymmetric conjugate addition of dialkylzinc reagents to unsaturated acylimidazoles followed by trapping of the intermediate zinc enolate with carbocations. The use of a chiral NHC ligand provides chiral zinc enolates in high enantiomeric purities. These enolates are reacted with highly electrophilic onium compounds to afford densely substituted acylimidazoles. DFT calculations helped to understand the reactivity of the zinc enolates derived from acylimidazoles and allowed their comparison with metal enolates obtained by other conjugate addition reactions.

Photochemically generated ionic species for cationic and step-growth polymerizations

Developing innovative photochemical methods for the purpose of attaining green chemistry and mitigating global warming has recently become a very important concept. While we have to move towards a more sustainable world, daily life is becoming increasingly dependent on the use of polymeric materials. Conventional thermal polymerization systems fail to fulfill the requirements of sustainable chemistry, resulting in an increase in energy demand. This article outlines cationic and step-growth polymerizations of various monomers initiated by different photochemically generated ionic species and their advantages over conventional polymerization systems. Typical examples of photoinduced cationic and step-growth polymerizations performed under UV, visible and near-infrared (NIR) light are summarized under two main categories; direct and indirect initiating systems. In direct initiating systems the use of commercially available and structurally modified onium salts as one-component photoinitiators for both polymerizations are summarized. Indirect initiating systems, proceeding through i) photoinduced electron/energy transfer (PET), ii) charge-transfer complexation and iii) free-radical promoted cationic polymerization (FRPCP), are summarized with a focus on the recent step-growth methods developed in our laboratory.

Proton conduction in tetra-n-butylammonium bromide semiclathrate hydrate

Clathrate hydrate as well as ice has been spotlighted as promising materials to investigate the properties of hydrogen-bonded networks formed by the water molecules. In the semiclathrate hydrate (SCH, a kind of clathrate hydrate) consisting of host water molecules and guest quaternary onium salts, the anion takes part in the hydrogen-bonded networks with the water molecules. In the present study, we measured the electrical conductivity and electrical relaxation time in the single-crystalline tetra-n-butylammonium bromide (TBAB) SCH by electrochemical impedance spectroscopy. The results clearly revealed that the conduction carrier was proton. The electrical relaxation time of proton conduction in TBAB SCH was similar to the reorientation time of the water molecules in TBAB SCH estimated by the results of nuclear magnetic resonance.

One-Pot Synthesis of CO2-Based Polylactide-b-Poly(ether carbonate)-b-Polylactide Triblock Copolymers and Their Mechanical Properties

The synthesis of CO2-based triblock copolymers made of a central poly(ether carbonate) blocks flanked by two external polylactide blocks is described. Such triblock copolymers are obtained in one-pot by first CO2/epoxides copolymerization using a difunctional onium salt initiator in the presence of triethylborane, followed by ring-opening polymerization (ROP) of lactide (LA) assisted by diphenylurea (UPh), a hydrogen-bonding activator. Upon varying the pressure of CO2 during its copolymerization with propylene oxide (PO), the Tg of the central block could be fine-tuned allowing the synthesis of poly(propylene oxide-co-propylene carbonate) (PPPC) with various carbonate versus ether contents. These PPPC samples are then mechanically characterized; as their content in ether linkages progressively increased, a transition from brittle-to-ductile-to-elastomeric behavior could be seen. Upon appending two external enantiomeric poly(d-lactide) (PDLA) blocks to the central PPPC block, the generated PDLA-b-PPPC-b-PDLA triblock copolymers exhibit an impressive increase of their ductility compared to that of the parent statistical PPPC copolymers. When benchmarked against commercial polyolefins the latter CO2-based triblock copolymers outperform the mechanical performances of high density polyethylene (HDPE) and low density polyethylene (LDPE) by all accounts, their elasticity modulus, tensile strength, toughness and elongation at break being indeed superior to those of the polyolefins tested.

Influence of bioactive particles and onium salt on the physicochemical properties of experimental infiltrants.

This study evaluated physicochemical properties of experimental infiltrants after addition of hydroxyapatite nanoparticles (HAp) or 58S bioactive glass (BAG) and diphenyliodonium hexafluorophosphate (DPI). The resin matrix was composed of TEGDMA/Bis-EMA (3:1), 0.5 mol% CQ, and 1 mol% EDAB. The blends received or not 0.5 mol% DPI and 10% wt BAG or HAp. Icon was used as commercial control. The groups were characterized by XRD, FT-IR spectrometry, and SEM before and after simulated body fluid (SBF) immersion for up to 7 days. Polymerization kinetics (n =3 ), water sorption and solubility (n=10), and viscosity (n = 3) were surveyed. For polymerization kinetics, the samples were polymerized for 5 min and the data were obtained from 40 s and 5 min. Statistical analysis was made using ANOVA and Tukey's test (a = 0.05). After 7 days of SBF immersion, XRD and FT-IR showed that the HAp crystalline phase was present only in the HAp groups. A lower degree of conversion (DC) and polymerization rate were observed for the Icon and BAG groups, whereas HAp showed higher values. For the BAG group, DPI increased polymerization rate and DC in 40 s. After 5 min, all groups presented DC above 80%. In groups with particles, the HAp groups exhibited higher viscosity, whereas DPI groups showed a decrease in viscosity. Icon had the highest water sorption. To conclude, BAG neither improved the physicochemical properties studied, nor did it show bioactive properties. The addition of DPI reduced viscosity caused by particle addition and also attenuated the DC decrease caused by BAG addition. The addition of bioactive particles to infiltrants should be seen with caution because they increase viscosity and may not bring major clinical improvements that justify their use. DPI might be indicated only if any component is added to the infiltrant to act as a compensation mechanism.

(Bipyridine bisphenolate)-aluminum/onium salt pair: a highly active binary catalyst for ring-opening polymerization of lactide with improved thermostability and protic tolerance

A series of bipyridine bisphenolate aluminum complexes with outstanding thermostability and tolerance to protic agents were synthesized and used to catalyze the ROP of LA with assist of onium salt as cocatalyst in epoxide.

Design of Thermoplastic Polyurethanes with Conferred Antibacterial, Mechanical, and Cytotoxic Properties for Catheter Application.

Thermoplastic polyurethanes (TPUs) are proposed as suitable solution for the fabrication of biocompatible catheters with appropriate mechanical parameters and confirmed antibacterial and cytocompatible properties. For this purpose, a series of quaternary ammonium salts (QASs) and quaternary phosphonium salts (QPSs) based monomers were prepared followed by the determination of their minimal inhibitory concentrations (MICs) against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Pseudomonas aeruginosa (P. aeruginosa). A combination of the most active ammonium (QAS-C14) and phosphonium (QPS-TOP) salts led to a MIC down to 2.4 μg/mL against S. aureus and 9 μg/mL against P. aeruginosa, corroborating the existence of a synergistic effect. These quaternary onium salt (QOS) units were successfully incorporated along the polymer chain, as part of a two-step synthesis approach. The resulting TPU-QOS materials were subsequently characterized through thermal, mechanical, and surface analyses. TPU-Mix (combining the most active QAS-C14 and QPS-TOP units) showed the highest antibacterial efficiency, confirming the synergistic effect between both QOS groups. Finally, an MTT assay on the SiHa cell line revealed the low cytotoxicity level of these polymeric films, making these materials suitable for biomedical application. To go one step further in the preindustrialization approach, proof of concept regarding the catheter prototype fabrication based on TPU-QAS/QPS was validated by extrusion.

A pyrrole–carbazole photoinitiator for radical and cationic visible light LED photopolymerization

Driven by the growing demand towards low cost and environmentally friendly curing processes, the synthesis of visible light absorbing photoinitiators has been a significant research direction in the field of photopolymerization in the past couple of years. Herein, a novel synthesis route is introduced to obtain a bifunctional pyrrole-carbazole-based photoinitiator (ECMO) via one-step reaction. On account of its excellent absorption at 405 nm and the ability for hydrogen donation, ECMO can initiate free radical polymerization upon visible light exposure and forms colorless photopolymers. Notably, ECMO is further able to act as sensitizer for triarysulfonium salts and significantly extends the absorption window of the onium salts into the visible light spectral region. ECMO sensitized triarysulfonium salts show superior curing performance in cationic polymerization (e.g. higher final monomer conversion) compared to conventional isopropylthioxanthone/triarysulfonium hexafluorophosphate systems. In addition, thermogravimetric analysis shows that ECMO possesses exceptional thermal stability, which facilitates its practical application in photopolymerization processes.