Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations.

Using a combination of liquid-phase X-ray spectroscopy experiments and small-scale calculations we have gained new insights into the speciation of halozincate anions in ionic liquids (ILs). Both core and valence X-ray photoelectron spectroscopy (XPS) experiments were performed directly on the liquid-phase ILs, supplemented by Zn 1s X-ray absorption near edge structure (XANES) spectroscopy. Density functional theory (DFT) calculations were carried out on both 1- and 2- halozincate anions, in both a generalised solvation model SMD (Solvation Model based on Density) and the gas phase, to give XP spectra and total energy differences; time-dependent DFT was used to calculate XANES spectra. Speciation judgements were made using a combination of the shape and width of the experimental spectra, and visual matches to the calculated spectra. For 2- halozincate anions, excellent matches were found between the experimental and calculated XP spectra, clearly showing that only 2- halozincate anions were present at all zinc halide mole fractions, x, studied. At specific values of x (0.33, 0.50, 0.60) only one halozincate anion was present; equilibria of different halozincate anions at those values of x were not observed. All findings show that chlorozincate anion and bromozincate anion speciation matched at the same x. Based on the results, predictions are made of the halozincate anion speciation for all values of x up to 0.67. Caution is advised when using differences in calculated total energies obtained from DFT to judge halozincate anion speciation, even when the SMD was employed, as predictions based on total energy differences did not always match the findings from the experimental and calculated spectra. Our findings clearly establish that the combination of high-quality experimental data from multiple spectroscopies and a wide range of calculated structures are essential to have high confidence in halozincate anion speciation identification.

Resonant X-ray photoelectron spectroscopy: identification of atomic contributions to valence states.

Valence electronic structure is crucial for understanding and predicting reactivity. Valence non-resonant X-ray photoelectron spectroscopy (NRXPS) provides a direct method for probing the overall valence electronic structure. However, it is often difficult to separate the varying contributions to NRXPS; for example, contributions of solutes in solvents or functional groups in complex molecules. In this work we show that valence resonant X-ray photoelectron spectroscopy (RXPS) is a vital tool for obtaining atomic contributions to valence states. We combine RXPS with NRXPS and density functional theory calculations to demonstrate the validity of using RXPS to identify atomic contributions for a range of solutes (both neutral and ionic) and solvents (both molecular solvents and ionic liquids). Furthermore, the one-electron picture of RXPS holds for all of the closed shell molecules/ions studied, although the situation for an open-shell metal complex is more complicated. The factors needed to obtain a strong RXPS signal are investigated in order to predict the types of systems RXPS will work best for; a balance of element electronegativity and bonding type is found to be important. Additionally, the dependence of RXPS spectra on both varying solvation environment and varying local-covalent bonding is probed. We find that RXPS is a promising fingerprint method for identifying species in solution, due to the spectral shape having a strong dependence on local-covalency but a weak dependence on the solvation environment.

A one-pot-one-reactant synthesis of platinum compounds at the nanoscale.

The preparation of inorganic nanomaterials with a desired structure and specific properties requires the ability to strictly control their size, shape and composition. A series of chemical reactions with platinum compounds carried out within the 1.5 nm wide channel of single-walled carbon nanotubes (SWNTs) have demonstrated the ability of SWNTs to act as both a very effective reaction vessel and a template for the formation of nanocrystals of platinum di-iodide and platinum di-sulphide, materials that are difficult to synthesise in the form of nanoparticles by traditional synthetic methods. The stepwise synthesis inside nanotubes has enabled the formation of Pt compounds to be monitored at each step of the reaction by aberration-corrected high resolution transmission electron microscopy (AC-HRTEM), verifying the atomic structures of the products, and by an innovative combination of fluorescence-detected X-ray absorption spectroscopy (FD-XAS) and Raman spectroscopy, monitoring the oxidation states of the platinum guest-compounds within the nanotube and the vibrational properties of the host-SWNT, respectively. This coupling of complementary spectroscopies reveals that electron transfer between the guest-compound and the host-SWNT can occur in either direction depending on the composition and structure of the guest. A new approach for nanoscale synthesis in nanotubes developed in this study utilises the versatile coordination chemistry of Pt which has enabled the insertion of the required chemical elements (e.g. metal and halogens or chalcogens) into the nanoreactor in the correct proportions for the controlled formation of PtI2 and PtS2 with the correct stoichiometry.

Quantitative adsorbate structure determination for quasicrystals using x-ray standing waves.

The quantitative structure determination of adsorbed species on quasicrystal surfaces has so far appeared to present insurmountable problems. The normal incidence standing x-ray wave field technique offers a simple solution, without extensive data sets or large computations. Its application to quasicrystals raises several conceptual difficulties that are related to the phase problem in x-ray diffraction. We demonstrate their solution for the case of Si atoms adsorbed on the decagonal Co-rich modification of the Al-Co-Ni quasicrystal to determine the local structure, comprising 6-atom clusters in particular hollow sites.

The vapour of imidazolium-based ionic liquids: a mass spectrometry study.

Eight common dialkylimidazolium-based ionic liquids have been successfully evaporated in ultra-high vacuum and their vapours analysed by line of sight mass spectrometry using electron ionisation. The ionic liquids investigated were 1-alkyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]imide, [C(n)C(1)Im][Tf(2)N] (where n = 2, 4, 6, 8), 1-alkyl-3-methylimidazolium tetrafluoroborate, [C(n)C(1)Im][BF(4)] (where n = 4, 8), 1-butyl-3-methylimidazolium octylsulfate, [C(4)C(1)Im][C(8)OSO(3)] and 1-butyl-3-methylimidazolium tetrachloroferrate, [C(4)C(1)Im][FeCl(4)]. All ionic liquids studied here evaporated as neutral ion pairs; no evidence of decomposition products in the vapour phase were observed. Key fragment cations of the ionised vapour of the ionic liquids are identified. The appearance energies, E(app), of the parent cation were measured and used to estimate the ionisation energies, E(i), for the vapour phase neutral ion pairs. Measured ionisation energies ranged from 10.5 eV to 13.0 eV. Using both the identity and E(app) values, the fragmentation pathways for a number of fragment cations are postulated. It will be shown that the enthalpy of vaporisation, Δ(vap)H, can successfully be measured using more than one fragment cation, although caution is required as many fragment cations can also be formed by ionisation of decomposition products.

Density and surface tension of ionic liquids.

We measured the density and surface tension of 9 bis[(trifluoromethyl)sulfonyl]imide ([Tf(2)N](-))-based and 12 1-methyl-3-octylimidazolium ([C(8)C(1)Im](+))-based ionic liquids (ILs) with the vibrating tube and the pendant drop method, respectively. This comprehensive set of ILs was chosen to probe the influence of the cations and anions on density and surface tension. When the alkyl chain length in the [C(n)C(1)Im][Tf(2)N] series (n = 1, 2, 4, 6, 8, 10, 12) is increased, a decrease in density is observed. The surface tension initially also decreases but reaches a plateau for alkyl chain lengths greater than n = 8. Functionalizing the alkyl chains with ethylene glycol groups results in a higher density as well as a higher surface tension. For the dependence of density and surface tension on the chemical nature of the anion, relations are only found for subgroups of the studied ILs. Density and surface tension values are discussed with respect to intermolecular interactions and surface composition as determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). The absence of nonvolatile surface-active contaminants was proven by ARXPS.

Insights into the surface composition and enrichment effects of ionic liquids and ionic liquid mixtures.

A systematic study of ionic liquid surfaces by angle resolved X-ray photoelectron spectroscopy (ARXPS) is presented. By reviewing recent and presenting new results for imidazolium-based ionic liquids (ILs), we discuss the impact of chemical differences on surface composition and on surface enrichment effects. (1) For the hydrophilic ethylene glycol (EG) functionalised ILs [Me(EG)MIm][Tf(2)N], [Et(EG)(2)MIm][Tf(2)N] and [Me(EG)(3)MIm][Tf(2)N], which vary in the number of ethylene glycol units (from 1 to 3), we find that the surface composition of the near-surface region is in excellent agreement with the bulk composition, which is attributed to attractive interactions between the oxygen atoms on the cation to the hydrogen atoms on the imidazolium ring. (2) For [C(n)C(1)Im][Tf(2)N] (where n = 1-16), i.e. ILs with an alkyl chain of increasing length, an enrichment of the aliphatic carbons is observed for longer chains (n > 2), at the expense of the polar cation head groups and the anions in the first molecular layer, both of which are located approximately at the same distance from the outer surface. (3) To study the influence of the anion on the surface enrichment, we investigated ten ILs [C(8)C(1)Im][X] with the same cation, but very different anions [X](-). In all cases, surface enrichment of the cation alkyl chains is found, with the degree of enrichment decreasing with increasing size of the anion, i.e., it is most pronounced for the smallest anions and least pronounced for the largest anions. (4) For the IL mixture [C(2)C(1)Im][Tf(2)N] and [C(12)C(1)Im][Tf(2)N] we find a homogeneous distribution in the outermost surface region with no specific enrichment of the [C(12)C(1)Im](+) cation.

Influence of different substituents on the surface composition of ionic liquids studied using ARXPS.

Angle resolved X-ray photoelectron spectroscopy has been used to study the surface composition of various nonfunctionalized and functionalized 1,3-dialkylimidazolium ionic liquids. For [CnC1Im][Tf2N] (where n = 2-16), an enrichment of the aliphatic carbon was observed for longer chains (n > or = 4). Enrichment of the aliphatic carbon also occurs for alkyl chains attached to the anion, as observed for [C2C1Im][OcOSO3]. Oligo(ethyleneglycol)ether (PEG) functionalities in the cation lead to a surface composition close to bulk stoichiometry and thus a loss in enrichment of the chains. This effect is attributed to attractive interactions between the oxygen atoms on the cation to the hydrogen atoms on the imidazolium ring for [Et(EG)2MIm] [Tf2N] and [Me(EG)3MIm][Tf2N].

Influence of different anions on the surface composition of ionic liquids studied using ARXPS.

Angle-resolved X-ray photoelectron spectroscopy has been used to study the influence of different types of anions on the surface composition of ionic liquids (ILs). We have investigated nine ILs with the same cation, 1-octyl-3-methylimidazolium [C(8)C(1)Im](+), but very different anions. In all cases, an enrichment of the cation alkyl chains is found at the expense of the polar cation head groups and the anions in the first molecular layer. This enhancement effect decreases with increasing size of the anion, which means it is most pronounced for the smallest anions and least pronounced for the largest anions. A simple model is proposed to explain the experimental observations.