Role Of Ion Pairs Research Articles

Role of ion pairs in model glycosylation reactions of permethylated glucosyl and xylosyl triflates

Elucidating the molecular mechanisms of chemical O-glycosylation remains a significant challenge in glycochemistry. This study examines the mechanism of the nucleophilic substitution reaction between glycosyl triflates, which are extensively used in studies of glycosylation mechanisms, and several acceptor alcohols. The investigation was conducted through a comparative analysis of permethylated glucosyl triflate GTf and its xylosyl counterpart XTf. The glycosylation reactions, conducted in dichloromethane using GTf and XTf with EtOH, tBuOH, and CF3CH2OH, exhibited diverse α/β selectivities depending on the types of donor and acceptor molecules used. Identifying a unified mechanism to explain this range of selectivities proved challenging. Notably, we observed a distinct trend wherein the addition of excess triflate salt (Bu4NOTf) had a more pronounced effect on the α/β selectivity in glycosylation reactions utilizing XTf compared to those using GTf. Quantum chemical calculations performed at the SCS-MP2//DFT(M06-2X) level, with explicit inclusion of five solvent molecules, showed that contact ion pairs arising from XTf were significantly more stable than those from GTf. These experimental and computational results strongly suggest that ion pairs play a more crucial role in the glycosylation process involving XTf than GTf. Additionally, our quantum chemical analyses clarified that the enhanced stability of the ion pairs from XTf was attributed not to the strength of the C-1−OTf bond within XTf but to the flexibility in the conformational changes of XTf's pyranosyl ring.

Influence of Ion Pairs and Activity on the Index of Irrigation Water Quality Relying on Some Modern Terms in Erbil Governorate. *

Influence of Ion Pairs and Activity on the Index of Irrigation Water Quality Relying on Some Modern Terms in Erbil Governorate. *

Impact of ionic liquid incorporation on ionic transport and dielectric properties of PEO-lithium salt-based quasi-solid-state electrolytes: role of ion-pairing

Impact of ionic liquid incorporation on ionic transport and dielectric properties of PEO-lithium salt-based quasi-solid-state electrolytes: role of ion-pairing

Investigation into dual emission of a cyclometalated iridium complex: The role of ion-pairing

Time-resolved emission of [Ir(ppy)2dcbpy]Cl (1a, ppy = 2-phenylpyridine, dcbpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) dissolved in DMF revealed a biexponential decay of the excited state. Prior studies on cyclometalated iridium complexes indicated that such dual emission behavior can be attributed to an impurity, compounds that have two LUMO states that are close in energy, or the presence of ion-pairing. To probe each of these effects, a series of homoleptic, Ir(ppy)3 (2), and heteroleptic complexes, [Ir(ppy)2dcbpy]X [X = PF6−(1b), BPh4−(1c)] and [Ir(ppy)2bpy]X [bpy = 2,2′-bipyridine, X = Cl− (3a) PF6−(3b)], were synthesized and photophysically characterized. Among these complexes, only 1a exhibited dual emission with the emission lifetimes of 430 ± 5 ns (80%) and 125 ± 6 ns (20%) in DMF. These lifetimes were further confirmed with the nanosecond transient absorption kinetics, indicating that the dual emission likely did not originate from an impurity. When probing the emission and absorption kinetics of the salts 1b and 1c only one lifetime of 550 ± 10 ns was observed, indicating that the short lifetime of the Cl− salt (1a) comes from a putative ion-paired complex. Density-Functional Theory (DFT) calculations on 1 and 2 fragments in DMF helped uncover the reason behind the ion-pair formation, with carboxyl substituents in 1a causing a loss in electron density on the 3,3′-position of dcbpy. Additionally, the loss in electron density was experimentally validated with 1H NMR, which showed a noticeable downfield shift of the 3,3′-protons in relative to the shifts in 1b and 1c. The data supports that the dual emission observed in 1a is not from two separately emissive states, rather from the dissociated and ion-paired complexes.

Mechanisms of Al3+ Dimerization in Alkaline Solutions.

The molecular speciation of aluminum (Al3+) in alkaline solutions is fundamental to its precipitation chemistry within a number of industrial applications that include ore refinement and industrial processing of Al wastes. Under these conditions, Al3+ is predominantly Al(OH)4-, while at high [Al3+] dimeric species are also known to form. To date, the mechanism of dimer formation remains unclear and is likely influenced by complex ion···ion interactions. In the present work, we investigate a suite of potential dimerization pathways and the role of ion pairing on energetics using static DFT calculations and DFT and density functional tight binding molecular dynamics. Specific cation effects imparted by the background electrolyte cations Na+, Li+, and K+ have been examined. Our simulations predict that, when the Al species are ion-paired with either cation, the formation of the oxo-bridged Al2O(OH)62- is favored with respect to the dihydroxo-bridged Al2(OH)82-, in agreement with previous spectroscopic work. The formation of both dimers first proceeds by bridging of two monomeric units via one hydroxo ligand, leading to a labile Al2(OH)82- isomer. The effect of contact ion pairing of Li+ and K+ on the dimerization energetics is distinctly more favorable than that of Na+, which may have an effect on further oligomerization.

Cation-Controlled Assembly of Polyoxotungstate-Based Coordination Networks.

The Preyssler polyoxoanion, [NaP5 W30 O110 ]14- ({P5 W30 }), is used as a platform for evaluating the role of nonbridging cations in the formation of transition-metal-bridged polyoxometalate (POM) coordination frameworks. Specifically, the assembly architecture of Co2+ -bridged frameworks is shown to be dependent on the identity and amount of alkali or alkaline-earth cations present during crystallization. The inclusion of Li+ , Na+ , K+ , Mg2+ , or Ca2+ in the framework synthesis is used to selectively synthesize five different Co2+ -bridged {P5 W30 } structures. The influence of the competition between K+ and Co2+ for binding to {P5 W30 } in dictating framework assembly is evaluated. The role of ion pairing on framework assembly structure and available void volume is discussed. Overall, these results provide insight into factors governing the ability to achieve controlled assembly of POM-based coordination networks.

Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

AbstractThe Preyssler polyoxoanion, [NaP5W30O110]14− ({P5W30}), is used as a platform for evaluating the role of nonbridging cations in the formation of transition‐metal‐bridged polyoxometalate (POM) coordination frameworks. Specifically, the assembly architecture of Co2+‐bridged frameworks is shown to be dependent on the identity and amount of alkali or alkaline‐earth cations present during crystallization. The inclusion of Li+, Na+, K+, Mg2+, or Ca2+ in the framework synthesis is used to selectively synthesize five different Co2+‐bridged {P5W30} structures. The influence of the competition between K+ and Co2+ for binding to {P5W30} in dictating framework assembly is evaluated. The role of ion pairing on framework assembly structure and available void volume is discussed. Overall, these results provide insight into factors governing the ability to achieve controlled assembly of POM‐based coordination networks.

Insight into the role of ion-pairing in the adsorption of imidazolium derivative-based ionic liquids by activated carbon

The association of the cation and anion of ionic liquids (ILs) dominates the absorbability of ILs by activated carbon (AC). Nevertheless, the mechanism behind the role of ion-pairs is largely unknown. In this study, the adsorption of a series of imidazolium derivative-based ILs by AC was involved in response to the octanol-water partition coefficient (KOW), hydrogen bonding acidity (α), ion-pair binding constants (KIP), binding energy of ion-pairs (Ebinding) and density functional theory (DFT) calculation of ILs. A significant positive correlation between lg KOW and Kd and between KIP and lg KOW was observed (p < 0.05). However, both Ebinding and α was inversely proportional to KIP. Hence, the substitution of oxygen-containing functional groups, such as carboxyethyl, 1-methoxyethyl, and 1-(ethoxycarbonyl)methyl, on imidazolium ring enhanced the hydrogen bond interaction with water molecules and then weakened the binding of imidazolium cation and [NTf2]−, thereby reducing the adsorption of ILs to AC. DFT calculation further revealed that the polar substitution improved the electron density and electronegativity of imidazolium skeleton. By contrast, the ILs functionalized with non-polar groups (e.g., butyl, allyl, and benzyl) generally displayed high KIP values and low α values. Consequently, the formation of hydrogen bond between the oxygen-containing functional groups of IL cation and water would facilitate the dissociation of IL ion-pairs and then decrease the adsorption of ILs on AC.

Strong enrichment of atmospherically relevant organic ions at the aqueous interface: the role of ion pairing and cooperative effects.

Surface affinity, orientation and ion pairing are investigated in mixed and single solute systems of aqueous sodium hexanoate and hexylammonium chloride. The surface sensitive X-ray photoelectron spectroscopy technique has been used to acquire the experimental results, while the computational data have been calculated using molecular dynamics simulations. By comparing the single solute solutions with the mixed one, we observe a non-linear surface enrichment and reorientation of the organic ions with their alkyl chains pointing out of the aqueous surface. We ascribe this effect to ion paring between the charged functional groups on the respective organic ion and hydrophobic expulsion of the alkyl chains from the surface in combination with van der Waals interactions between the alkyl chains. These cooperative effects lead to a substantial surface enrichment of organic ions, with consequences for aerosol surface properties.

Remarkably selective NH4+ binding and fluorescence sensing by tripodal tris(pyrazolyl) receptors derived from 1,3,5-triethylbenzene: structural and theoretical insights on the role of ion pairing

Differences in pyrazole substitution result in dramatic changes in NH4+ binding and fluorescence sensing, due to ion pairing and solvation effects.

Role of Ion-Pairs in Brønsted Acid Catalysis

Phosphoric acids have emerged as efficient organo-catalysts for various reactions. Despite widespread use, details of the reaction intermediates giving rise to stereocontrol have remained elusive. To clarify the nature of the catalyst–substrate interaction, we characterize and quantify catalyst–substrate complex formation by combining dielectric spectroscopy, quantum chemistry, and 1H NMR spectroscopy. For a series of different solvents, the interaction between substrate and catalyst is dominated by ion-pairing, rather than hydrogen bonding, at ambient conditions. Correlation of ion association with catalytic enantioselectivity provides evidence that close-contact ion-pairing is essential for stereocontrol and that dissociation into free ions dramatically reduces enantioselectivity.

The role of ion pairs and ion activity in classification of ground waters for irrigation in Erbil plain

The role of ion pairs and ion activity in classification of ground waters for irrigation in Erbil plain

Simulations of photoemission and equilibrium redox processes of ionic liquids: the role of ion pairing and long-range polarization

We have studied oxidation and reduction of ionic liquids using methods of theoretical chemistry. In particular, we have modeled photoelectron spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf(2)N]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf(2)N]) ionic liquids and their components. We have considered ion pairs in the gas phase and solvated in the water represented by a dielectric continuum. We have also characterized the isolated cation and anion of the ionic liquids. The calculated quantities have been compared with available experiments. The photoelectron spectra were modeled within linearized reflection approximation, using a composite ab initio approach based on combination of the MP2 method for the ground state, the PMP2 method for the first ionized electronic state and the TDDFT method to estimate the higher ionization energies. We have also briefly explored energetics of processes following the vertical electron attachment/detachment. Our calculations were able to reproduce the measured photoelectron spectra. We have shown that the valence photoelectron spectrum results from simultaneous ionization from many molecular orbitals. In the threshold region, the electron is ejected from the anion in the gas phase ion pair while the cationic moiety is ionized when the ion pair is solvated. We have investigated the effect of both short-range and long-range interactions on the ionization characteristics, showing that the long-range polarization of the solvent effectively screens the specific short-range interactions. The large difference between the HOMO-LUMO gap and the electrochemical window has been rationalized in terms of relaxation following the redox processes, i.e. solute and solvent geometric relaxation and reactions, e.g. dimerization of the imidazolium radical formed during the reduction.

The Role of Ion Pairs in the Second‐Order NLO Response of 4‐X‐1‐Methylpiridinium Salts

A series of 4-X-1-methylpyridinium cationic nonlinear optical (NLO) chromophores (X = (E)-CH=CHC(6)H(5); (E)-CH=CHC(6)H(4)-4'-C(CH(3))(3); (E)-CH=CHC(6)H(4)-4'-N(CH(3))(2); (E)-CH=CHC(6)H(4)-4'-N(C(4)H(9))(2); (E,E)-(CH=CH)(2)C(6)H(4)-4'-N(CH(3))(2)) with various organic (CF(3)SO(3)(-), p-CH(3)C(6)H(4)SO(3)(-)), inorganic (I(-), ClO(4)(-), SCN(-), [Hg(2)I(6)](2-)) and organometallic (cis-[Ir(CO)(2)I(2)](-)) counter anions are studied with the aim of investigating the role of ion pairing and of ionic dissociation or aggregation of ion pairs in controlling their second-order NLO response in anhydrous chloroform solution. The combined use of electronic absorption spectra, conductimetric measurements and pulsed field gradient spin echo (PGSE) NMR experiments show that the second-order NLO response, investigated by the electric-field-induced second harmonic generation (EFISH) technique, of the salts of the cationic NLO chromophores strongly depends upon the nature of the counter anion and concentration. The ion pairs are the major species at concentration around 10(-3) M, and their dipole moments were determined. Generally, below 5x10(-4) M, ion pairs start to dissociate into ions with parallel increase of the second-order NLO response, due to the increased concentration of purely cationic NLO chromophores with improved NLO response. At concentration higher than 10(-3) M, some multipolar aggregates, probably of H type, are formed, with parallel slight decrease of the second-order NLO response. Ion pairing is dependent upon the nature of the counter anion and on the electronic structure of the cationic NLO chromophore. It is very strong for the thiocyanate anion in particular and, albeit to a lesser extent, for the sulfonated anions. The latter show increased tendency to self-aggregate.

A Theoretical Study of SN2′ Reactions of Allylic Halides: Role of Ion Pairs

Various disparate experimental results are explained by the hypothesis that reactions of anionic nucleophiles with allylic halides are generally S(N)2. The S(N)2' reactions that do occur proceed generally with anti stereochemistry. Reactions with ion pair nucleophiles occur preferentially as S(N)2' reactions with syn stereochemistry. This hypothesis is consistent with a variety of computations at the HF, B3LYP, mPW1PW91 and MP2 levels with the 6-31+G(d) basis set of reactions of Li and Na fluoride and chloride with allyl halides and 4-halo-2-pentenes. Solvation is considered by a combination of coordination of dimethyl ether to the lithium and sodium cations and "dielectric solvation" with a polarized continuum model.

Ion pairs and their role in modulating stability of cold‐ and warm‐active uracil DNA glycosylase

MD simulations and continuum electrostatics calculations have been used to study the observed differences in thermostability of cold- and warm-active uracil DNA glycosylase (UDG). The present study focuses on the role of ion pairs and how they affect the thermal stability of the two enzymes. Analysis of the MD generated structural ensembles show that cod UDG (cUDG) and human UDG (hUDG) have 11 and 12 ion pairs which are present in at least 30% of the conformations. The electrostatic contribution of the ion pairs, computed using continuum electrostatics, is slightly more favorable in cUDG at 298 K. This is primarily attributed to more optimized interactions between the ion pairs and nearby dipoles/charges in cUDG. More global salt bridges are found in hUDG and are more stabilizing when compared to cUDG, possibly playing a role in maintaining overall stability and reducing conformational entropy. Both enzymes contain one three-member ionic network, but the one found in hUDG is far more stabilizing. Our results also suggest that care should be taken when performing statistical analysis of crystal structures with respect to ion pairs, and that crystallization conditions must be carefully examined when performing such analysis.

Progress and challenges in polyoxometalate-based catalysis and catalytic materials chemistry

The impact of early transition-metal oxygen-anion cluster (polyoxometalate or “POM”) geometric and electronic structural properties on POM-based catalysis is addressed. Three specific areas of general challenge in POM-based catalysis and catalytic materials are elaborated: (1) the role of ion pairing in catalyst stability, selectivity, and reactivity; (2) the presence of multiple reactive forms of the POMs and the interconvertability of these forms under turnover conditions; and (3) the impact of POM ground state and excited state electronic structure on turnover and selectivity.

Effects of Strong Ion‐Pairing on the Electrochemical Reduction of Cyclooctatetraene in Tetrahydrofuran in the Presence of Lithium Ion. Peak Coalescence Does Not Imply Potential Inversion

AbstractThe first study of the voltammetric reduction of cyclooctatetraene (COT) in tetrahydrofuran (THF) in the presence of lithium ion is reported. A single wave is observed at −2.23 V vs. Ag/0.1 M AgNO3. Density functional calculations have been carried out on a variety of COT/Li/THF species in order to clarify the nature and role of ion pairing in this system. The dominant species in solution are the COT/Li/(THF)2 anion radical and the COT/Li2/(THF)4 dianion. Computer simulations have been carried out to further understand the effects of ion pairing on the reduction. The simulations show that coalescence of two waves into one can occur in the presence of strong ion pairing even when the second reduction potential is negative of the first.

Mass and Charge Transport in a Cross-Linked Polyether-Based Electrolyte. The Role of Ion Pairs

In an amorphous solid polymer electrolyte the positive and negative ions are found to move much faster in the form of neutral pairs than individually. Although the fraction of ion pairs turns out to be small (less than 10%), the ion pairs provide the most significant contribution to the transport of cations being crucial for battery operation. This is a striking new result of a detailed comparison of tracer diffusion experiments and electrical conductivity measurements made on a cross-linked random copolymer of ethylene oxide and propylene oxide complexed with sodium iodide. The study utilizes radioactive isotopes of sodium and iodine in tiny amounts to trace the diffusivity of both ion species individually. The overall charge diffusivity due to the joint effect of cations and anions is monitored by impedance spectroscopy. A thorough evaluation of the experimental data shows that the diffusivity of all mobile species, although different in magnitude, shows the same temperature dependence. This is a conseq...

Role of ion pairing in anionic additive effects on the separation of cationic drugs in reversed-phase liquid chromatography

Mobile phase additives can significantly affect the separation of cationic drugs in reversed-phase liquid chromatography (RPLC). Although there are many applications for anionic additives in RPLC separations, the retention mechanism of basic drugs in the presence of inorganic and highly hydrophilic anionic species in the mobile phase is not at all well understood. Two major retention mechanisms by which anionic additives can influence the retention of cations are: (1) ion pair formation in the mobile phase with subsequent retention of the neutral ion pair; (2) pre-sorption of anionic additives on the stationary phase followed by “dynamic ion-exchange” or “electrostatic interaction” with the analytes. Because the use of ion pair chromatography in the separation of proteins, peptides, and basic drugs is rapidly increasing, understanding the retention mechanism involved is becoming more important, especially for the smaller commonly used hydrophilic anionic additives (e.g., formate HCOO −, chloride Cl −, trifluoroacetate CF 3COO −, perchlorate ClO 4 −, and hexafluorophosphate PF 6 −). In this work, we compared various anionic additives in light of their effects on the retention of basic drugs. As did many others we found that the addition of anionic additives (Cl −, CF 3COO −, ClO 4 −, PF 6 −) profoundly influences the retention of basic drugs. In order to explain the data and differentiate the mechanisms by which the anionic additives perturb the chromatography, we used ion pair formation constants independently measured by capillary electrophoresis (CE) under the mobile phase conditions (pH, solvent composition) identical to those used in chromatography. Agreement between the predicted and experimental chromatographic data under various conditions was evaluated. Under specific circumstances (e.g., pH, stationary phase, and nature of anionic additive), we conclude that the ion pair mechanism is more important than the dynamic ion-exchange and at other conditions it remains a significant contribution.