Na<Superscript>+</Superscript>/K<Superscript>+</Superscript> selectivity in the formation of ion pairs in aqueous solutions

The integral equations of liquids (RISM) and molecular dynamics method were used to calculate the mean force potential for the SO₃ and COO hydrophilic groups and the CH₃ hydrophobic group in the acetate, methyl sulfonate, and hydrosulfate anions, which form ion pairs with sodium and potassium cations in water. The carboxyl group selectively binds sodium ions from solutions containing Na⁺ and K⁺ ions, in spite of their equal charges, because the potassium ion experiences stronger steric hindrances near this group compared with sodium. The biophysical consequences of the revealed selectivity are discussed.     

Solvation structure of magnesium,zinc, and alkaline earth metal ions in N,N‐dimethylformamide,N,N‐dimethylacetamide,and their mixtures studied by means of Raman spectroscopy and DFT calculations—Ionic size and electronic effects on steric congestion

The solvation structure of magnesium, zinc(II), and alkaline earth metal ions in N,N‐dimethylformamide (DMF) and N,N‐dimethylacetamide (DMA), and their mixtures has been studied by means of Raman spectroscopy and DFT calculations. The solvation number is revealed to be 6, 7, 8, and 8 for Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, respectively, in both DMF and DMA. The δ (O C N) vibration of DMF shifts to a higher wavenumber upon binding to the metal ions and the shift Δν(= ν_bound − ν_free) becomes larger, when the ionic radius of the metal ion becomes smaller. The ν (N CH₃) vibration of DMA also shifts to a higher wavenumber upon binding to the metal ions. However, the shift Δν saturates for small ions, as well as the transition‐metal (II) ions, implying that steric congestion among solvent molecules takes place in the coordination sphere. It is also indicated that, despite the magnesium ion having practically the same ionic radius as the zinc(II) ion of six‐coordination, their solvation numbers in DMA are significantly different. DFT calculations for these metalsolvate clusters of varying solvation numbers revealed that not only solvent–solvent interaction through space but also the bonding nature of the metal ion plays an essential role in the steric congestion. The individual solvation number and the Raman shift Δν in DMF–DMA mixtures indicate that steric congestion is significant for the magnesium ion, but not appreciable for calcium, strontium, and barium ions, despite the solvation number of these metal ions being large. Copyright © 2006 John Wiley & Sons, Ltd.     

Influence of salts of 1,1,2,2-tetrachloroethane on the acidity function of the solutions of methanesulfonic acid

The influence of salts CH₃SO₃Na and/or CH₃SO₃Bu₄N on the acidity function H ₀ of methanesulfonic acid (MSA) and its solutions in water, N,N-dimethylformamide (DMF) in mixtures of methanesulfonic acid-N,N-dimethylformamide MSA-DMF ≤ 1 and ethyl acetate (EA) in a mixture of methanesulfonic acid-ethyl acetate MSA/EA (1: 1) and 1,1,2,2-tetrachloroethane (TCE) on H ₀ of methanesulfonic acid (MSA) and its mixtures with N,N-dimethylformamide (DMF), 2-pyrrolidine (Pyr) and ethyl acetate (EA) with the ratios of MSA: DMF equal to 1: 1 and 2: 1, MSA: Pyr (2: 1) and MSA: EA, equal to 2: 1, 1: 1, and 1: 2 is investigated by the indicator method at 25°C. It is revealed that a change in the acidity of the solutions of MSA in the aprotic solvents can occur as a result of the influence of salts both on the equilibrium composition of the nascent complexes and on their ionizing ability (both of these factors change acidity on addition of salts to the mixture of MSA-EA (1: 1)). An explanation is proposed why CH₃SO₃Na and CH₃SO₃Bu₄N influence differently on the acidity of aqueous solutions of MSA. It is established that in the solutions of (TCE) the ionizing ability of MSA and its complexes with DMF, Pyr and EA, which have different degree of the proton transfer ($ K_{T_i } $ K_{T_i } ), depends on the concentration ratio of MSA: TCE and ($ K_{T_i } $ K_{T_i } ): TCE.     

Structure of complexes in the H<Subscript>2</Subscript>SO<Subscript>4</Subscript>—2-pyrrolidone system as determined by IR-spectroscopy and quantum-chemical calculations

Specific features of complexation in solutions of a strong dibasic acid in the H₂SO₄–2-pyrrolidone (Pyr) system (in the range of compositions of 0–100% H₂SO₄) are studied using multiple frustrated total internal reflection IR spectroscopy. The conclusions drawn on the structure of the complexes formed in such solutions are confirmed by quantum-chemical calculations of the mPyr · nH₂SO₄ (m, n = 1, 2) heteroassociates and by comparison of their calculated and measured vibrational spectra. It is found that, in the investigated solutions, four types of acid–base complexes, with various degrees of proton transfer in the OHO bridge, are formed: (AHA)^– anions with quasi-symmetric H-bonds, solvated by acid molecules, or entering into the composition of PyrH⁺ · (AHA)^– ion pairs; quasi-ion pairs with incomplete proton transfer to the base molecule of 1: 1 and 2: 2 compositions; and 2Pyr · H₂SO₄ complexes with two O–H···O bridges of molecular type. The main differences in the mechanisms of the acid–base interactions in the H₂SO₄–Pyr system as compared to the CH₃SO₃H–Pyr system result from the participation of two OH-groups of H₂SO₄ molecule in these interactions. Therefore, two types of quasi-ion pairs and complexes of 2Pyr · H₂SO₄ composition are formed.     

Polymer–ion–clay interaction based model for ion conduction in intercalation-type polymer nanocomposite

A series of polymer nanocomposite films based on intercalation of (PAN)₈LiCF₃SO₃ into the nanometric clay channels of an organomodified clay has been prepared using the standard solution-casting technique. The role of organoclay concentration on polymer–ion interaction, ion–ion interaction, and ion–clay interaction in clay-based nanocomposite films has been analyzed using Fourier transform infrared (FTIR) analysis. Substantial ion dissociation is observed even at a very low clay loading (1–2 wt.%) in the nanocomposites. FTIR results suggest the presence of both uncoordinated CF₃SO₃ ⁻ (free-anions) and ion pairs in the nanocomposite evidenced by changes in CF₃SO₃ ⁻ symmetry from C3ν to Cs and marked asymmetry in the profile of degenerate δ_d(CF₃ ⁻) mode. The experimental results suggest a direct correlation of clay-assisted ion dissociation process with variation in conductivity (σ _dc) and glass transition temperature (T _g) as a function of clay concentration. A model has been proposed to explain the observed correlation on the basis of polymer–ion–clay interaction. The proposed scheme of ion transport mechanism appears to be consistent with the experimental observation.     

The structural transformation of monoclinic [(R)-C5H14N2][Cu(SO4)2(H2O)4]·2H2O into orthorhombic [(R)-C5H14N2]2[Cu(H2O)6](SO4)3: crystal structures and thermal behavior

Single crystals of [(R)-C₅H₁₄N₂][Cu(SO₄)₂(H₂O)₄]·2H₂O (1) were grown through the slow evaporation of a solution containing H₂SO₄, (R)-C₅H₁₂N₂ and CuSO₄·5H₂O. These crystals spontaneously transform to [(R)-C₅H₁₄N₂]₂[Cu(H₂O)₆](SO₄)₃ (2) over the course of four days at room temperature. The same single crystal on the same mounting was used for the determination of the structure of (1) and the unit cell determination of (2). A second single crystal of the transformed batch has served for the structural determination of (2). Compound 1 crystallizes in the noncentrosymmetric space group P2₁ (No. 4) and consists of trimeric [Cu(SO₄)₂(H₂O)₄]^2? anions, [(R)-C₅H₁₄N₂]²⁺ cations and occluded water molecules. Compound 2 crystallizes in P2₁2₁2 (No. 18) and contains [Cu(H₂O)₆]²⁺ cations, [SO₄]^2? anions and occluded water molecules. The thermal decompositions of compounds 1 and 2 were studied by thermogravimetric analyses and temperature-dependent X-ray diffraction.     

Solvolytic reactivity of pyridinium ions

The leaving group abilities of pyridine, 4‐methylpyridine, and 4‐chloropyridine in S_N1 solvolytic reactions have been determined by analyzing the rate constants of X,Y‐substituted benzhydrylpyridinium salts obtained in various solvents. By applying the linear free energy relationship equation, log k = s_f (E_f + N_f), the nucleofuge specific parameters of 4‐substituted pyridine have been extracted. Because of solvation in the reactant ground state, the reactivity (nucleofugality, N_f) of a given pyridine decreases as the polarity of the solvent increases. High slope parameters (s_f > 1) may be due to the spread of the energy levels of the benzhydrylium ion/pyridine pair intermediates in comparison to benzhydrylium ion/chloride pairs (s_f ≈ 1). Because of slow heterolysis step of pyridinium salts in various solvents, some are stable under normal conditions. Copyright © 2015 John Wiley & Sons, Ltd.     

Solvation energy of multiply charged anions and dielectric constant for finite system: a microscopic theory based bottom-up and top-down approach

This is the first time a microscopic theory-based bottom-up approach has been implemented to derive an analytical expression for the solvation energy for a finite (N) system, including the bulk. This bottom-up approach provides the information on solvation energies of anionic solutes in finite-size clusters, including the bulk (N = ∞), from the knowledge of the detachment energies for the system containing a few numbers of solvent molecules. However, in the case of dielectric constant, a microscopic theory-based top-down approach has been prescribed to derive an analytical expression for the static dielectric constant for the finite system. In this approach, the knowledge of the dielectric constant for the bulk provides a scheme to obtain the same quantity for a wide numbers of solvent molecules. As an illustrative example, the hydrated doubly charged anions, SO^?2 ₄.NH₂O and C₂O^?2 ₄.NH₂O, have been considered, and the calculated bulk solvation energy for the SO^?2 ₄.NH₂O system is found to be in very good agreement (within 5%) with the available experimental result. However, the same quantity calculated based on the Born model is found to be largely deviating (32%) from the experimental result. The calculated results of the dielectric constant for these two systems support the linear theory of dielectric constant.     

Gas‐phase acidity of bis[(perfluoroalkyl)sulfonyl]imides. Effects of the perfluoroalkyl group on the acidity

The gas‐phase acidity (GA) values were determined for a number of perfluoroalkyl‐substituted sulfonylimides by measuring proton‐transfer equilibria using a Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometer. The GA scale below 286.5 kcal mol^?1 for (CF₃SO₂)₂NH was extended and partially revised. The GA value of (C₄F₉SO₂)₂NH which is currently the strongest acid was revised from 284.1 to 278.6 kcal mol^?1. The effect of fluorine atoms on the acidity of perfluoroalkyl‐substituted sulfonylimides was described with the following model where N_(α), N_(β), N_(γ), and N_(δ) are the numbers of fluorine atoms at α, β, γ, and δ position in R_fSO₂ (R_f = perfluoroalkyl group), respectively. This correlation indicates that the electron‐withdrawing ability of the R_fSO₂ group can be described in terms of the number of fluorine atoms in the perfluoroalkyl group corrected by taking into account their positions. Copyright © 2014 John Wiley & Sons, Ltd.     

Basicity of trifluoromethylsulfonylformamidines. DFT and FTIR study and NBO analysis

The effect of the electron–acceptor substituent CF₃SO₂ at the imine nitrogen atom on the basicity and the electron distribution in N,N‐alkylformamidines ( 1 , 2 , 3 , 4 , 5 ) was studied experimentally by the FTIR spectroscopy and theoretically at the DFT (B3LYP/6‐311+G(d,p)) level of theory, including the natural bond orbital (NBO) analysis. The calculated proton affinities of the imine nitrogen atom and the sulfonyl oxygen (PA_N′ and PA_O) depend on the atomic charges, the C?N′ and N′―S bond polarity and on the energy of interaction of the amine nitrogen and the oxygen lone pairs with antibonding π* and σ*‐orbitals. The basicity of the imine nitrogen atom is increased with the increase of the electron‐donating power of the substituent at the amine nitrogen atom due to stronger interaction n_N → π*_C?N′, but is decreased for the electron‐withdrawing groups MeSO₂ and CF₃SO₂ at the imine nitrogen atom in spite of the increase of this conjugation. Protonation of ( 1 , 2 , 3 , 4 , 5 ) in CH₂Cl₂ solution in the presence of CF₃SO₃H occurs at the imine nitrogen atom, while the formation of hydrogen bonds with 4‐fluorophenol takes place at the sulfonyl oxygen atom, whose basicity is lower than that of N,N′‐dimethylmethanesulfonamide but higher than of N,N′‐dimethyltrifluoromethanesulfonamide. Copyright © 2015 John Wiley & Sons, Ltd.     

The electronic structure of the nitridoosmate(VIII) ion,OsO3N-

The electronic spectrum of the nitridoosmate(VIII) ion, OsO₃N^-, has been measured at liquid helium temperatures for thin films of the n-tetrabutyl-ammonium salt and for oriented, doped LiClO₄. 3H₂O single crystals. Four structured band systems, all individually composed of superimposed A ₁ ← A ₁ and E←A ₁ transitions, are observed at energies comparable to those of the two lowest ¹ T ₂←¹ A ₁ transitions of OsO₄. Prominent vibronic structure assigned to ν(Os-N) is observed for all of the bands. The bands are assigned to transitions to completely spin-orbit mixed states. The highest filled orbitals of OsO₃N^- are oxygen-localized and π non-bonding. The nitrido ligand appears to ‘dominate’ the π-bonding in the ion.     

Conductivities and ion association constants of ferric chloride and chromic chloride in DMF and DMSO as a function of temperature

The equivalent conductivities of anhydrous ferric chloride (FeCl₃) and anhydrous chromic chloride (CrCl₃) were measured in nonaqueous aprotic solvents such as N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) at temperatures between 278.15 and 318.15 K. In both DMF and DMSO, conductivity values for FeCl₃ were found to be higher than those for CrCl₃. In addition, the conductivity values for both FeCl₃ and CrCl₃ in DMF were higher than those in DMSO at all temperatures. The conductivity data were analyzed by the Robinson–Stokes equations. The limiting equivalent ionic conductivities for ferric ion (Fe³⁺) and chromic ion (Cr³⁺) and the ion association constants (K _A ) for FeCl₃ and CrCl₃ were determined in DMF and DMSO. The K _A values calculated for both FeCl₃ and CrCl₃ in DMF were higher than those in DMSO. This can be ascribed to an increase of the ion association constants with a decrease of the relative permittivity of solvents used in this study. The K _A values increased with the increase in temperature in the studied solvents. Thermodynamic functions (Gibbs’ free energy, entropy, and enthalpy of ion association) were estimated from the temperature dependence of the ion association constant. The positive values of entropy and enthalpy found for FeCl₃ and CrCl₃ at all temperatures indicate that the association process in DMF and DMSO is endothermic.     

Detailed analysis of the charge transfer complex N,N‐dimethylaniline–SO2 by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N‐dimethylaniline (DMA) and sulfur dioxide (SO₂). The formation of a deep red oil by the reaction of SO₂ with DMA is an evidence of the charge transfer (CT) nature of the DMA–SO₂ interaction. The DMA–SO₂ normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm⁻¹, which are enhanced when resonance is approached. These bands are assigned to ν_s(SO₂) and ν(ϕ N) vibrational modes, respectively, confirming the interaction between SO₂ and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO₂ with the ring π electrons, which gives rise to a π–π* low‐energy CT electronic transition, as confirmed by time‐dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA–SO₂ spectrum at the B3LYP/6‐311 + + g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO₂. Copyright © 2009 John Wiley & Sons, Ltd.     

Electron paramagnetic resonance of spin-variable metallomesogens [Fe<Emphasis Type="Italic">L</Emphasis><Subscript>2</Subscript>]<Emphasis Type="Italic">X</Emphasis> (<Emphasis Type="Italic">X</Emphasis> = PF<Subscript>6</Subscript>, SCN)

Significant differences in the manifestation of spin-crossover properties of the mesogen compounds [FeL ₂]X with oxysalicylidene-N′-ethyl-N-ethylenediamine ligands L and anions X = PF₆⁻ and SCH⁻ have been found by means of electron paramagnetic resonance. The electron paramagnetic resonance data and the quantum-chemical calculation within the density functional theory enables us to establish that the observed specific features are associated with the incorporation of the SCH⁻ ion into the first coordination sphere of the Fe(III) ion. The role of the transition of the material to the liquid-state phase in the formation of a low-dimensional (two-dimensional) structure with stronger intermolecular interactions has been revealed.     

Non-perturbative gravitational corrections in a class of N = 2 string duals

We investigate the non-perturbative equivalence of some heterotic/type II dual pairs with N = 2 supersymmetry. The perturbative heterotic scalar manifolds are respectively SU(1, 1)/U(1) × SO(2,2+N_V)/SO(2) × SO(2+N_V) and SO(4,4+N_H)/SO(4) × SO(4+N_H) for moduli in the vector multiplets and hypermultiplets. The models under consideration correspond, on the type II side, to self-mirror Calabi-Yau threefolds with Hodge numbers h^1,1 = N_V + 3 = h^2,1 = N_H + 3, which are K3 fibrations. We consider three classes of dual pairs, with N_V = N_H = 8, 4 and 2. The models with h^1,1 = 7 and 5 provide new constructions, while the h^1,1 = 11, already studied in the literature, is reconsidered here. Perturbative R²-like corrections are computed on the heterotic side by using a universal operator whose amplitude has no singularities in the (T, U) space, and can therefore be compared with the type II side result. We point out several properties connecting K3 fibrations and spontaneous breaking of the N = 4 supersymmetry to N = 2. As a consequence of the reduced S- and T- duality symmetries, the instanton numbers in these three classes are restricted to integers, which are multiples of 2, 2 and 4, for N_V = 8, 4 and 2, respectively.     

Photoproduction of Boson Pairs in a Radiation-Dominated Universe. II

The average number of pairs of scalar massive particles produced by a decaying photon in a radiation-dominated universe is calculated. The dependence of the expression obtained on the energy of the initial photon is investigated. Numerical estimates are found for the formative time t ₀ of the processes of decay of photons in an early universe and for the total number N ^(±) _{out pair} of photoproduced scalar pairs. The estimates are: t ₀ 3 min and N ^(±) _{out pair} 10³¹·N ^(±) ₀(0), where N ^(±) ₀(0) is the total number of pairs produced from the vacuum of a free quantized field.     

Spectroscopic and ab initio characterization of the conformational states of the bis(perfluoro‐ ethanesulfonyl)imide anion (BETI−)

Ab initio calculations were combined with infrared and Raman studies to spectroscopically distinguish the two conformers of the BETI⁻ or bis(perfluoroethanesulfonyl)imide anion, [N(SO₂C₂F₅)₂]⁻, as was previously done for [N(SO₂CF₃)₂]⁻, the TFSI⁻ anion. BETI⁻ is predicted to exist, as does TFSI⁻, in two conformational states of C₂ and C₁ symmetries, the former being more stable by about 6 kJ mol⁻¹. This conformational isomerism produces weak Raman splittings that can be resolved only at low temperatures. Thus, solutions of LiBETI with glymes cooled down to 113 K exhibit a very intense Raman doublet at ∼745–740 cm⁻¹ characteristic of a quenched conformational equilibrium between the C₂ and C₁ conformers. Annealing of the (G3)₂:LiBETI solvate, where G3 is triglyme, leads to an ordered crystalline phase with all the anions in the C₂ conformation, as in the reference salt Me₄NBETI. This conclusion cannot be extended to all the systems in which the BETI⁻ anion interacts weakly with the cation, however, since the diglyme solvate, (G2)₂:LiBETI, contains both C₁ and C₂ anion conformers (in 2:1 ratio) at low temperatures independent of the sample's thermal history. The conformational splittings are larger in infrared, as illustrated by two absorption bands at 601 and 615 cm⁻¹ associated with the C₂ and C₁ anion conformers, respectively. It is possible to follow the relative intensities of these bands in a LiBETI solution with diglyme above room temperature up to 387 K. The C₂ conformer is found to be more stable than C₁ by 4.7 ± 0.7 kJ mol⁻¹. Copyright © 2006 John Wiley & Sons, Ltd.     

Coordination of Eu3+ in mono-urethane cross-linked hybrid xerogels

A novel family of Eu³⁺-doped hybrid materials namedmono-urethanesils is investigated. The host organic/inorganic matrix, preparedvia the sol-gel process, is a siliceous network to which methyl end-capped pendant oligopolymer chains containing seven oxyethylene units are covalently bonded by means of urethane cross-links, -NHC(=O)O-. The lanthanide cations have been introduced as europium triflate, Eu(CF₃SO₃)₃. The xerogels have been identified by the designation m-Ut(350)_nEu(CF₃SO₃)₃, where Ut represents the urethane linkages, 350 indicates the average molecular weight of the organic component and n denotes the number of (OCH₂CH₂) repeat units per Eu³⁺ ion. The mono-urethanesil samples examined, with compositions ranging between n=∞ and 40, are totally amorphous. The spectral and thermal data provide conclusive evidence that in these materials the lanthanide ions are preferentially coordinated by the carbonyl oxygens of the urethane moieties, rather than by the ether oxygens of the polymer chains. The location of the characteristic bands of the triflate ions in the FTIR spectra of these Eu³⁺-based xerogels indicates that the anions interact weakly with the cations over the entire range of guest salt concentration studied. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Real Forms of Quantum Orthogonal Groups,q-Lorentz Groups in any Dimension

We review known real forms of the quantum orthogonal groups SO _q (N). New *-conjugations are then introduced and we contruct all real forms of quantum orthogonal groups. We thus give an RTT formulation of the *-conjugations on SO _q (N) that is complementary to the U _q (g) *-structure classification of Twietmeyer. In particular, we easily find and describe the real forms SO _q (N-1,1) for any value of N. Quantum subspaces of the q-Minkowski space are analyzed.     

Free-field realization of theWKP(N) algebra

TheW _KP ^(N) algebra has been identified with the second Hamiltonian structure in theNth Hamiltonian pair of the KP hierarchy. In this Letter, by constructing the Miura map that decomposes the second Hamiltonian structure in theNth pair of the KP hierarchy, we show thatW _KP ^(N) can also be decomposed toN independent copies ofW _KP ⁽¹⁾ algebras, therefore its free-field realization can be worked out by constructing free fields for each copy ofW _KP ⁽¹⁾ . In this way, the free fields may consist ofN + 2n number of bosons, among them, 2n are in pairs, wheren is an arbitrary integer between 1 andN. We also express the currents ofW _KP ^(N) in terms of the currents ofN —n copies of U(1) andn copies of SL(2,R) _k algebras with levelk = 1. By reductions, we give similar results forW ^(N) andW ₃ ⁽²⁾ algebra.