Structural and electric field effects of ions in aqueous nanodrops

Ensemble infrared photodissociation (IRPD) spectra in the hydrogen stretch region (～2950-3800 cm(-1)) are reported for M(H(2)O)(35-37), with M = I(-), Cl(-), HCO(3)(-), OH(-), tetrabutyl-, tetrapropyl-, and tetramethylammonium, Cs(+), Na(+), Li(+), H(+), Ba(2+), Ca(2+), Co(2+), Mg(2+), La(3+), and Tm(3+), at 133 K. A single, broad feature is observed in the bonded-OH region of the spectra that indicates that the water network in these clusters is bulk-like and likely resembles liquid water more strongly than ice. The free-OH region for all of these clusters is dominated by peaks corresponding to water molecules that accept two and donate one hydrogen bond (AAD water molecules), indicating that AAD water molecules are more abundant at the surface of these ions than AD water molecules. A-only water molecules are present in significant abundance only for the trivalent metal cations. The frequency of the AAD free-OH stretch band shifts nearly linearly with the charge state of the ion, consistent with a Stark shift attributable to the ion's electric field. From these data, a frequency range of 3704.9-3709.7 cm(-1) is extrapolated for the free-OH of AAD water molecules at the (uncharged) bulk liquid water surface, consistent with sum-frequency generation spectroscopy experiments. Differences in both the bonded- and the free-OH regions of the spectra for these ions are attributable to ion-induced patterning of the water network that extends to the surface of the clusters, which includes water molecules in the third and fourth solvation shells; that is, these ions pattern water molecules at long distance to various extents. These spectra are simulated using two different electrostatic models previously used to calculate OH-stretch spectra of bulk water and aqueous solutions and parametrized for bonded-OH frequencies. These models qualitatively reproduce a number of features in the experimental spectra, although it is evident that more sophisticated treatment of water molecule and ion polarizability and vibrational coupling is necessary for more quantitative comparisons.     

Ions in size-selected aqueous nanodrops: sequential water molecule binding energies and effects of water on ion fluorescence

The effects of water on ion fluorescence were investigated, and average sequential water molecule binding energies to hydrated ions, M(z)(H(2)O)(n), at large cluster size were measured using ion nanocalorimetry. Upon 248-nm excitation, nanodrops with ~25 or more water molecules that contain either rhodamine 590(+), rhodamine 640(+), or Ce(3+) emit a photon with average energies of approximately 548, 590, and 348 nm, respectively. These values are very close to the emission maxima of the corresponding ions in solution, indicating that the photophysical properties of these ions in the nanodrops approach those of the fully hydrated ions at relatively small cluster size. As occurs in solution, these ions in nanodrops with 8 or more water molecules fluoresce with a quantum yield of ~1. Ce(3+) containing nanodrops that also contain OH(-) fluoresce, whereas those with NO(3)(-) do not. This indirect fluorescence detection method has the advantages of high sensitivity, and both the size of the nanodrops as well as their constituents can be carefully controlled. For ions that do not fluoresce in solution, such as protonated tryptophan, full internal conversion of the absorbed 248-nm photon occurs, and the average sequential water molecule binding energies to the hydrated ions can be accurately obtained at large cluster sizes. The average sequential water molecule binding energies for TrpH(+)(H(2)O)(n) and a doubly protonated tripeptide, [KYK + 2H](2+)(H(2)O)(n), approach asymptotic values of ~9.3 (n ≥ 11) and ~10.0 kcal/mol (n ≥ 25), respectively, consistent with a liquidlike structure of water in these nanodrops.     

Coordination numbers of hydrated divalent transition metal ions investigated with IRPD spectroscopy

Hydration of the divalent transition metal ions, Mn, Fe, Co, Ni, Cu, and Zn, with 5-8 water molecules attached was investigated using infrared photodissociation spectroscopy and photodissociation kinetics. At 215 K, spectral intensities in both the bonded-OH and free-OH stretch regions indicate that the average coordination number (CN) of Mn(2+), Fe(2+), Co(2+), and Ni(2+) is ~6, and these CN values are greater than those of Cu(2+) and Zn(2+). Ni has the highest CN, with no evidence for any population of structures with a water molecule in a second solvation shell for the hexa-hydrate at temperatures up to 331 K. Mn(2+), Fe(2+), and Co(2+) have similar CN at low temperature, but spectra of Mn(2+)(H(2)O)(6) indicate a second population of structures with a water molecule in a second solvent shell, i.e., a CN < 6, that increases in abundance at higher temperature (305 K). The propensity for these ions to undergo charge separation reactions at small cluster size roughly correlates with the ordering of the hydrolysis constants of these ions in aqueous solution and is consistent with the ordering of average CN values established from the infrared spectra of these ions.     

Observation of the first hydration layer of isolated cations and anions through the FTIR-ATR difference spectra

The attenuated total reflectance-Fourier transform infrared (ATR-FTIR) difference spectra of the dilute aqueous (NH4)2SO4, Na2SO4, MgSO4, ZnSO4, NaClO4, and Mg(ClO4)2 solutions by pure water were obtained at various concentrations. In the difference spectra of aqueous (NH4)2SO4 solutions, a peak at approximately 3039 cm(-1), two shoulders at approximately 3155 and approximately 2894 cm(-1), and a peak at approximately 1445 cm(-1) were ascribed to N-H stretching and bending vibrations, respectively. A small negative peak was resolved at approximately 3660 cm(-1) in the difference spectra of (NH4)2SO4, which is the sole contribution of SO4(2-) either in the O-H stretching or in the O-H bending region. The positive peaks of the difference spectra in the O-H stretching region for Na2SO4, MgSO4, and ZnSO4 systems, which constantly appeared at approximately 3423, approximately 3136, and approximately 3103 cm(-1) respectively, were suggested to be the contribution of the interactions between metal cations (Na+, Mg2+, and Zn2+) and water molecules, especially from the first hydrated layer of the cations. In the region of 800-1200 cm(-1), the normally infrared-prohibited nu1 (SO4(2-)) band was observed as a weak peak at approximately 981 cm(-1) even at very dilute concentrations (0.10 mol dm(-3)) due to the disturbance of the water molecules hydrated with SO4(2-), even though such a feature may increasingly result from associated ions with increasing concentration. The spectra of the water molecules directly influenced by ClO4-, i.e., mostly the first layer of hydrated water, in NaClO4 and Mg(ClO4)2 solutions were obtained by subtracting the corresponding spectra of the same metal sulfate solutions at the same concentrations from the perchlorate solutions. A positive peak at approximately 3583 +/- 6 cm(-1) and a negative peak at approximately 3184 +/- 25 cm(-1) were obtained as the result of the subtraction. The positive peak was attributed to the water molecules weakly hydrogen-bonded with ClO4-, while the negative one to the reduction of water molecules with fully hydrogen-bonded five-molecule tetrahedral nearest neighbor structure on the introduction of ClO4-.     

Metal complexes of tetrapodal ligands: synthesis, spectroscopic and thermal studies, and X-ray crystal structure studies of Na(I), Ca(II), Sr(II), and Ba(II) complexes of tetrapodal ligands N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine

Twelve complexes 1-12 of general category [M(ligand)(anion)(x)(water)(y)], where ligand = N,N,N',N'-tetrakis(2-hydroxypropyl/ethyl)ethylenediamine (HPEN/HEEN), anion = anions of picric acid (PIC), 3,5-dinitrobenzoic acid (DNB), 2,4-dinitrophenol (DNP), and o-nitrobenzoic acid (ONB), M = Ca(2+), Sr(2+), Ba(2+), or Na(+), x = 1 and 2, and y = 0-4, were synthesized. All of these complexes were characterized by elemental analysis, IR, (1)H and (13)C NMR, and thermal studies. X-ray crystal studies of these complexes 1-12, [Ca(HPEN)(H(2)O)(2)](PIC)(2).H(2)O (1), [Ca(HEEN)(PIC)](PIC) (2), Ba(HPEN)(PIC)(2) (3), [Na(HPEN)(PIC)](2) (4), Ca(HPEN)(H(2)O)(2)](DNB)(2).H(2)O (5),Ca(HEEN)(H(2)O)](DNB)(2).H(2)O (6), [Sr(HPEN)(H(2)O)(3)](DNB)(2) (7), [Ba(HPEN)(H(2)O)(2)](DNB)(2).H(2)O](2) (8), [[Ba(HEEN)(H(2)O)(2)](ONB)(2)](2) (9), [[Sr(HPEN)(H(2)O)(2)](DNP)(2)](2) (10), [[Ba(HPEN)(H(2)O)(2)](DNP)(2)](2) (11), and [Ca(HEEN)(DNP)](DNP) (H(2)O) (12), have been carried out at room temperature. Factors which influence the stability and the type of complex formed have been recognized as H-bonding interactions, presence/absence of solvent, nature of the anion, and nature of the cation. Both the ligands coordinate the metal ion through all the six available donor atoms. The complexes 1 and 5-11 have water molecules in the coordination sphere, and their crystal structures show that water is playing a dual character. It coordinates to the metal ion on one hand and strongly hydrogen bonds to the anion on the other. These strong hydrogen bonds stabilize the anion and decrease the cation-anion interactions by many times to an extent that the anions are completely excluded out of the coordination sphere and produce totally charge-separated complexes. In the absence of water molecules as in 2 and 3 the number of hydrogen bonds is reduced considerably. In both the complexes the anions case interact more strongly with the metal ion to give rise to a partially charge-separated 2 or tightly ion-paired 3 complex. High charge density Ca(2+) forms only monomeric complexes. It has more affinity toward stronger nucleophiles such as DNP and PIC with which it gives partially charge-separated eight-coordinated complexes. But with relatively weaker nucleophile like DNB, water replaces the anion and produces a seven coordinated totally charge-separated complex. Sr(2+) with lesser charge/radius ratio forms only charge-separated monomeric as well as dimeric complexes. Higher coordination number of Sr(2+) is achieved with coordinated water molecules which may be bridging or nonbridging in nature. All charge-separated complexes of the largest Ba(2+) are dimeric with bridging water molecules. Only one monomeric ion-paired complex was obtained with Ba(PIC)(2). Na(+) forms a unique dinuclear cryptand-like complex with HPEN behaving as a heptadentate chelating-cum-bridging ligand.     

Surface Complexation Modeling of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) Ion Adsorption on Silica Gel

Surface complex formation of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) ions was determined on the surface of silica gel. Experimental data obtained by acid-base titration of suspensions were interpreted in terms of the triple-layer model. The value of the deprotonation constant of surface OH could be determined precisely but the protonation constant was rather uncertain. The logarithms of ion pair formation constants for K(+), NO(3)(-), Ca(2+), and SO(4)(2-) adsorbed in the beta-plane are log K(ipM,X) approximately 0, therefore these species can be considered inert ions in the investigated pH range. F(-), Co(2+), and Cr(3+) ions were found to be strongly sorbed in the o-plane. In order to provide a good fit and to obtain parameters independent of their initial values, all possible equilibrium must be accounted for in the models. Copyright 2001 Academic Press.     

Direct observation of triple ions in aqueous solutions of nickel(II) sulfate: a molecular link between the gas phase and bulk behavior

Electrospray ionization of an aqueous solution of nickel(II) sulfate provides direct experimental evidence for the formation of triple ions of the type [Ni(2)(SO(4))(H(2)O)(n)](2+) and [Ni(SO(4))(2)](2-), whose existence in aqueous solution has previously been proposed based on relaxation spectroscopy [Chen et al. J. Sol. Chem. 2005, 34, 1045]. Formally, these triple ions are formed by aggregation of the solvated ions Ni(2+) and SO(4)(2-), respectively, with the neutral ion pair NiSO(4). In addition, also higher adducts are observed, e.g. the "pentuple ions" [Ni(3)(SO(4))(2)(H(2)O)(n)](2+) (n = 7-9) and [Ni(2)(SO(4))(3)](2-), of which the dicationic is extensively hydrated, whereas the anionic is not. The structures of the dinuclear nickel clusters are derived from ab initio calculations and their infrared spectra are compared with experimental data obtained for the gaseous ions [Ni(2)SO(4)(H(2)O)(5)](2+) and [Ni(2)(SO(4))(3)](2-), respectively. The calculations show that the structures are crucially controlled by the degree of solvation of nickel ion. Explicit consideration of solvating water molecules within the first coordination sphere suggest that the dicationic triple ion [Ni(2)SO(4)](aq)(2+) is bent and thus bears a permanent dipole moment, whereas the [Ni(SO(4))(2)](aq)(2-) dianion tends to be quasi-linear. The experimental and theoretical data for the gaseous ions thus support the elegant, but indirect, deductions previously made based on solution-phase studies.     

Structure and magnetism of the tetra-copper(II)-substituted heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8-)

The novel heteropolyanion [Cu(4)K(2)(H(2)O)(8)(alpha-AsW(9)O(33))(2)](8)(-) (1) has been synthesized and characterized by IR spectroscopy, elemental analysis, and magnetic studies. Single-crystal X-ray analysis was carried out on [K(7)Na[Cu(4)K(2)(H(2)O)(6)(alpha-AsW(9)O(33))(2)].5.5H(2)O](n)(K(7)Na-1), which crystallizes in the tetragonal system, space group P42(1)m, with a = 16.705(4) A, b = 16.705(4) A, c = 13.956(5) A, and Z = 2. Interaction of the lacunary [alpha-AsW(9)O(33)](9)(-) with Cu(2+) ions in neutral, aqueous medium leads to the formation of the dimeric polyoxoanion 1 in high yield. Polyanion 1 consists of two alpha-AsW(9)O(33) units joined by a cyclic arrangement of four Cu(2+) and two K(+) ions, resulting in a structure with C(2)(v)() symmetry. All copper ions have one terminal water molecule, resulting in square-pyramidal coordination geometry. Three of the copper ions are adjacent to each other and connected via two micro(3)-oxo bridges. EPR studies on K(7)Na-1 and also on Na(9)[Cu(3)Na(3)(H(2)O)(9)(alpha-AsW(9)O(33))(2)].26H(2)O (Na(9)-2) over 2-300 K yielded g values that are consistent with a square-pyramidal coordination around the copper(II) ions in 1 and 2. No hyperfine structure was observed due to the presence of strong spin exchange, but fine structure was observed for the excited (S(T) = 3/2) state of Na(9)-2 and the ground state (S(T) = 1) of K(7)Na-1. The zero-field (D) parameters have also been determined for these states, constituting a rare case wherein one observes EPR from both the ground and the excited states. Magnetic susceptibility data show that Na(9)-2 has antiferromagnetically coupled Cu(2+) ions, with J = -1.36 +/- 0.01 cm(-)(1), while K(7)Na-1 has both ferromagnetically and antiferromagnetically coupled Cu(2+) ions (J(1) = 2.78 +/- 0.13 cm(-)(1), J(2) = -1.35 +/- 0.02 cm(-)(1), and J(3) = -2.24 +/- 0.06 cm(-)(1)), and the ground-state total spins are S(T) = 1/2 in Na(9)-2 and S(T) = 1 in K(7)Na-1.     

Change of electrical conductivities between hydrated and dehydrated samples of honeycomb sheet structures with mixed oxidation state paddlewheel dirhodium complexes and halide ions

A series of mixed oxidation state compounds, [{Rh(2)(acam)(4)}(3)(μ(3)-X)(2)]·nH(2)O (Hacam = acetamide; X = Cl, n = 4 (1·4H(2)O); X = Br, n = 10 (2·10H(2)O); X = I, n = 10 (3·10H(2)O)) and [{Rh(2)(pram)(4)}(3)(μ(3)-X)(2)]·6H(2)O (Hpram = propionamide; X = Cl (4·6H(2)O), Br (5·6H(2)O), I (6·6H(2)O)) were synthesized and their X-ray structures were determined. In the crystal structure of all of these complexes, dirhodium complexes and halide ions construct 2-D honeycomb sheet arrangements in which the walls consist of Rh(2) units and halide ions lie at the corners. Complexes 1·4H(2)O, 4·6H(2)O, 5·6H(2)O and 6·6H(2)O have three independent Rh(2) units, in which there are two Rh(2)(5+) and one Rh(2)(4+). In these structures, the water molecules hydrogen bond to O atoms and from the N atoms of the amidate ligands. The number of hydrogen bonds from water molecules to the Rh(2)(4+) unit is greater than that to the Rh(2)(5+) units. This suggests that there exists pinning of the oxidation states by water molecules. In the structures of 2·10H(2)O and 3·10H(2)O, all of the Rh(2) units are crystallographically equivalent. In these structures, eight of the 10 water molecules form a honeycomb-like network between the {Rh(2)(acam)(4)}(3)X(2) honeycomb sheets. The former four structures show very low electrical conductivities of ca. 10(-8) S cm(-1) (room temperature, pellets) and the latter structures have the higher values of ca. 10(-4) S cm(-1). In the former complexes, improvement of the values to 10(-6) S cm(-1) was observed, caused by loss of pinning water.     

Ion condensation behavior and dynamics of water molecules surrounding the sodium poly(methacrylic acid) chain in water: a molecular dynamics study

All-atom molecular dynamics simulations are used to study the condensation behavior of monovalent (Na(+)) and multivalent (Ca(2+)) salt counterions associated with the co-ions (Cl(-)) surrounding the charged poly(methacrylic acid) (PMAA) chain in water. The study is extended to the influences on chain conformation, local arrangement, and dynamics of water in the highly diluted aqueous solutions. We find that even when the salt ions are monovalent, they attract more than one charged monomer and act as a bridging agent within the chain, as the multivalent salt ions. In principle, the salt ions bridge between not only the "non-adjacent" but also the "adjacent" charged monomers, leading to a more coil-like and a locally stretched conformation, respectively. With an increase in the salt concentration, the amount of coiled-type condensed ions increase and reach a maximum when the chain conformation becomes the most collapsed; whereas, the stretched-type shows an opposite trend. Our results show that the attractive interactions through the condensed salt ions between the non-adjacent monomers are responsible for the conformational collapse. When the salt concentration increases high enough, a significant increase for the stretched-type condensed ions makes an expansion effect on the chain. These stretched-type salt ions, followed by the adsorption of the co-ions and water molecules, tend to form a multilayer organization outside surrounding the PMAA chain. Thus, the expansion degree of the chain conformation is greatly limited. When only the monovalent Na(+) ions are present in the solutions, water molecules are primarily adsorbed into either the condensed Na(+) ions or the COO(-) groups. These adsorbed water molecules form hydrogen bonds with each other and enhance the local bridging behavior associated with the Na(+) condensation on the resultant chain conformation. With an increase in the amount of multivalent Ca(2+) salt ions, more water molecules are bonded directly with the condensed Ca(2+) ions. In this case, only the condensed Ca(2+) ions provide a strong bridging effect within the polymer chain. We observe a significant shift towards a higher frequency of the oxygen vibration spectrum and only a slight shift towards a higher frequency of the hydrogen spectrum for the water molecules associated with the ion condensation.     

Solvation of copper(II) sulfate in binary water/N,N-dimethylformamide mixtures: from the solution to the gas phase

The solvation of copper(II) sulfate in binary mixtures of water and N,N-dimethylformamide (DMF) is studied by a combined approach using electrochemical studies in solution and a mass spectrometric assay of the solvated ions formed from these solutions upon electrospray ionization (ESI). In the condensed phase, the limiting transference numbers (t(+/-)(o)) and the apparent ion association constants (K(A)'s) of CuSO(4) have been determined in water/DMF solutions at 20 degrees C. The t(+)(o) values decrease with increasing DMF content, demonstrating a gradual solvation of Cu(2+) by DMF molecules. The association constants indicate that aggregation becomes more pronounced as the DMF content increases. In order to achieve complementary insight, the intrinsic interactions among the ions and solvent molecules are investigated in gas-phase experiments of the CuSO(4)/water/DMF system using ESI mass spectrometry. Under the conditions used, the dications [Cu(DMF)(n)](2+) (n = 3-6), [Cu(2)(DMF)(n)SO(4)](2+) (n = 2-7), and [Cu(3)(DMF)(n)(SO(4))(2)](2+) (n = 2-7), and the monocations [Cu(OH)(DMF)(n)](+), [Cu(DMF)(n)(HSO(4))](+) (both, n = 1-3), and [Cu(DMF)(n)](+) (n = 1, 2), are formed as the leading copper-containing cations. Likewise, polynuclear copper clusters observed in the anion ESI spectra support partial aggregation occurring in solution. The gas-phase studies clearly support the conclusions that (i) DMF is a highly preferred ligand for CuII in comparison to water and that (ii) DMF supports ion association for which the mass spectrometric data suggest the formation of polynuclear copper clusters.     

Al3+, Ca2+, Mg2+, and Li+ in aqueous solution: calculated first-shell anharmonic OH vibrations at 300 K

The anharmonic OH stretching vibrational frequencies, ν(OH), for the first-shell water molecules around the Li(+), Ca(2+), Mg(2+), and Al(3+) ions in dilute aqueous solutions have been calculated based on classical molecular dynamics (MD) simulations and quantum-mechanical (QM) calculations. For Li(+)(aq), Ca(2+)(aq), Mg(2+)(aq), and Al(3+)(aq), our calculated IR frequency shifts, Δν(OH), with respect to the gas-phase water frequency, are about -300, -350, -450, and -750?cm(-1), compared to -290, -290, -420, and -830?cm(-1) from experimental infrared (IR) studies. The agreement is thus quite good, except for the order between Li(+) and Ca(2+). Given that the polarizing field from the Ca(2+) ion ought to be larger than that from Li(+)(aq), our calculated result seems reasonable. Also the absolute OH frequencies agree well with experiment. The method we used is a sequential four-step procedure: QM(electronic) to make a force field+MD simulation+QM(electronic) for point-charge-embedded M(n+) (H(2)O)(y) (second?shell) (H(2)O)(z) (third?shell) clusters+QM(vibrational) to yield the OH spectrum. The many-body Ca(2+)-water force-field presented in this paper is new. IR intensity-weighting of the density-of-states frequency distributions was carried out by means of the squared dipole moment derivatives.     

Characterization of hydrated Na+(phenol) and K+(phenol) complexes using infrared spectroscopy

Hydrated alkali metal ion-phenol complexes were studied to model these species in aqueous solution for M=Na and K. IR predissociation spectroscopy in the O-H stretch region was used to analyze the structures of M+(Phenol)(H2O)n cluster ions, for n = 1-4. The onset of hydrogen bonding was observed to occur at n=4. Ab initio calculations were used to qualitatively explore the types of hydrogen-bonded structures of the M+(Phenol)(H2O)4 isomers. By combining the ab initio calculations and IR spectra, several different structures were identified for each metal ion. In contrast to benzene, detailed in a previous study of Na+(Benzene)n(H2O)m [J. Chem. Phys. 110, 8429 (1999)], phenol is able to bind directly to Na+ even in the presence of four waters. This is likely the result of the sigma-type interaction between the phenol oxygen and the ion. With K+, the dominant isomers are those in which the phenol O-H group is involved in a hydrogen bond with the water molecules, while with Na+, the dominant isomers are those in which the phenol O-H group is free and the water molecules are hydrogen-bonded to each other. Spectra and ab initio calculations for the M+(Phenol)Ar cluster ions for M=Na and K are reported to characterize the free phenol O-H stretch in the M+(Phenol) complex. While pi-type configurations were observed for binary M+(Phenol) complexes, sigma-type configurations appear to dominate the hydrated cluster ions.     

Indirect spectrophotometric determination of sulphide with the ternary complex system Ag(I)-phen-BPR

Trace amounts of sulphide can be determined from its effect on the ternary complex system of Ag(+), Bromopyrogallol Red (BPR), and 1,10-phenanthroline (phen). Sulphide in the range 5-120 ng/ml causes a decrease in absorption, that is a linear function of the concentration. Common metal ions such as Na(+), K(+), Ca(2+), Mg(2+), Al(3+), Mn(2+) and anions such as F(-), Cl(-), NO(-)(3), SO(2-)(4), CO(2-)(3), and PO(3-)(4) at the 4 mug/ml level or more do not interfere, but I(-) or CN(-) must be absent.     

Flexibility of CuCl4-tetrahedra in bis[cinchoninium tetrachlorocuprate(II)]trihydrate single crystals. X-ray diffraction and EPR studies

Crystal structure of bis[cinchoninium tetrachlorocuprate(II)] trihydrate, [(C19H24N2O)CuCl4]2-3H2O, has been determined by X-ray diffraction at 100 K and reexamined at 293 K. The compound crystallizes in orthorhombic system with a P2(1)2(1)2(1) space group and unit cell parameters a = 15.3031(14), b = 36.415(3), and c = 7.8341(5) A at 100 K, and Z = 4. The asymmetric unit consists of two (CuCl4)(2-) tetrahedral anions linked by hydrogen bonds to two doubly protonated cinchonine molecules and three water molecules. The tetrahedra are strongly flattened, to approximately D(2d) symmetry, with different deformation for two inequivalent (CuCl4)(2-) -ions in the asymmetric unit. The deformation of (CuCl4)(2-) and cinchoninium cations varies with temperature due to a rearrangement of the bifurcated hydrogen bond network. This is a continuous process observed as a monotonic variation of the EPR spectral parameters and the unit cell dimensions. EPR spectra show that very weak exchange coupling J(12) = 0.0030 cm(-1) operates between Cu(2+) ions within asymmetric units, corresponding to the general formula of the compound, as well as between equivalent Cu(2+) sites of different molecules, whereas the coupling is negligible between inequivalent sites. The intermolecular J(12) coupling is temperature-independent indicating that the whole asymmetric unit behaves as a magnetic unit (pseudodimer) in the whole temperature range.     

3d-Metal derivatives of the [Cu(I)(SO3)4]7- ion: structure and magnetism

The Cu(SO(3))(4)(7-) anion, which consists of a tetrahedrally coordinated Cu(I) centre coordinated to four sulfur atoms, is able to act as a multidentate ligand in discrete and infinite supramolecular species. The slow oxidation of an aqueous solution of Na(7)Cu(SO(3))(4) yields a mixed oxidation state, 2D network of composition Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O. The addition of Cu(II) and 2,2'-bipyridine to an aqueous Na(7)Cu(SO(3))(4) solution leads to the formation of a pentanuclear complex of composition {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(+); a combination of hydrogen bonding and π-π stacking interactions leads to the generation of infinite parallel channels that are occupied by disordered nitrate anions and water molecules. A pair of Cu(SO(3))(4)(7-) anions each act as a tridentate ligand towards a single Mn(II) centre when Mn(II) ions are combined with an excess of Cu(SO(3))(4)(7-). An anionic pentanuclear complex of composition {[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)} is formed when Fe(II) is added to a Cu(+)/SO(3)(2-) solution. Hydrated ferrous [Fe(H(2)O)(6)(2+)] and sodium ions act as counterions for the complexes and are responsible for the formation of an extensive hydrogen bond network within the crystal. Magnetic susceptibility studies over the temperature range 2-300 K show that weak ferromagnetic coupling occurs within the Cu(II) containing chains of Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O, while zero coupling exists in the pentanuclear cluster {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(NO(3))·H(2)O. Weak Mn(II)-O-S-O-Mn(II) antiferromagnetic coupling occurs in Na(H(2)O)(6){[Cu(I)(SO(3))(4)][Mn(II)(H(2)O)(2)](3)}, the latter formed when Mn was in excess during synthesis. The compound, Na(3)(H(2)O)(6)[Fe(II)(H(2)O)(6)](2){[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)}·H(2)O, contained trace magnetic impurities that affected the expected magnetic behaviour.     

Protonated clathrate cages enclosing neutral water molecules: (H+)(H2O)21 and (H+)(H2O)28

This paper describes a systematic study on the clathrate structure of (H+)(H2O)21 using tandem mass spectrometry, vibrational predissociation spectroscopy, Monte Carlo simulations, and density functional theory calculations. We produced (H+)(H2O)n from a continuous corona-discharged supersonic expansion and observed three anomalies simultaneously at the cluster temperature near 150 K, including (1) the peak at n=21 is more intense than its neighboring ions in the mass spectrum, (2) the size-dependent dissociation fractions show a distinct drop for the 21-mer, and (3) the infrared spectrum of (H+)(H2O)21 exhibits only a single feature at 3699 cm(-1), corresponding to the free-OH stretching of three-coordinated water molecules. Interestingly, the anomalies appear or disappear together with cluster temperature, indicating close correlation of these three observations. The observations, together with Monte Carlo simulations and density functional theory calculations, corroborate the notion for the formation of a distorted pentagonal dodecahedral (5(12)) cage with a H2O molecule in the cage and a H3O+ ion on the surface for this "magic number" water cluster ion. The dodecahedral cage melts at higher temperatures, as evidenced by the emergence of a free-OH stretching feature at 3717 cm(-1) for the two-coordinated water in (H+)(H2O)21 produced in a warmer molecular beam. Extension of this study to larger clusters strongly suggests that the experimentally observed isomer of (H+)(H2O)28 is most likely to consist of a distorted protonated pentakaidecahedral (5(12)6(3)) cage enclosing two neutral water molecules.     

Chronocoulometric determination of nitrate on silver electrode and sodium hydroxide electrolyte

An electrochemical system that consists of a silver electrode in 0.01 M sodium hydroxide electrolyte was investigated in an effort to develop a sensitive in situ analytical method for nitrate. Cyclic voltammetry demonstrated that the proposed system has a high normalized sensitivity (2.47 A s(1/2) V(-1/2) M(-1) cm(-2)), compared to more complex electroanalytical schemes. Double-potential-step chronocoulometry was used to maximize the signal-to-noise ratio (SNR), and minimize interference from dissolved oxygen in the electrolyte. The integration period for double-potential-step chronocoulometry was determined by optimizing the extended Cottrell equation. The integrated current is proportional to nitrate up to 10 mM and the average detection limit is approximately 1.7 microM. Dissolved oxygen does not degrade performance. To examine the potential interference of other ions when analyzing nitrate, we measured the electrode response to 1000 microM each of NO(2-), Cl(-), PO(4)(3-), SO(4)(2-), F(-), CO(3)(2-), BO(2-), K(+), Ca(2+), and Sr(2+) with and without 1000 microM nitrate. Interference is negligible for most of the ions when nitrate is absent (i.e. <1% of the response to equimolar nitrate). However, interference is substantial (>20% increase or decrease in the electrode response to nitrate) for PO(4)(3-), Ca(2+), and Sr(2+) when equimolar nitrate is present.     

First steps towards dissolution of NaSO4- by water

NaSO(4)(-)(H(2)O)(n) (n = 0-4) clusters have been generated in the gas phase as model systems to simulate the first dissolution steps of sulfate salts in water; photoelectron spectroscopy and theoretical calculations indicate that the first three water molecules strongly interact with both Na(+) and SO(4)(2-), forming a three-water solvation ring to start to pry apart the Na(+)SO(4)(2-) contact ion pair.     

The single-crystal, basal face of ice I(h) investigated with sum frequency generation

Sum frequency generation spectroscopy has been used to investigate the hydrogen-bonded region of single-crystal, hexagonal ice in the temperature range of 113-178 K. The temperature and polarization dependences of the signal are used in conjunction with a recent theoretical model to suggest an interpretation of the bluest and reddest of the hydrogen-bonded peaks. The reddest feature is associated with strong hydrogen bonding; the dynamic polarizability of this feature is primarily parallel to the surface. It is assigned to a cooperative motion among the companion to the free-OH and four-coordinate oscillators hydrogen bonded to dangling lone-pair molecules on the surface. The bluest hydrogen-bonded feature is similarly assigned to a cooperative motion of the OH stretch of dangling lone-pair molecules and of four-coordinate molecules in the lower half bilayer that are hydrogen bonded to free-OH molecules. Reconstruction induced strain is present at as low as 113 K. These results provide a richer picture of the ice surface than has heretofore been possible.