Ionogels are an emerging class of soft material with exceptional properties stemming from high ionic liquid content. In contrast to other gel systems, the ionic liquid component provides an extra level of design. However, this highly modular nature has yet to be fully explored and the role ionic liquids play in the structural properties of gel-based materials is poorly understood. Here, methodical small angle neutron scattering and X-ray photoelectron spectroscopy studies reveal the relationship between bulk structure and surface composition of a soft material for the first time. Furthermore, we show how ionic liquid design dictates polymer structure, which in turn can be harnessed to fine tune the mechanical properties of ionogels. With a level of control over gel structure beyond what is possible using molecular solvents, our systematic study thus provides insight into how ionic liquids can expand the design space for gel development for a broad range of applications.

We report a wide Q-range neutron diffraction study on the absorption of oxygen molecules into deuterated ZIF-8 as the system is taken through its gate-opening transition by applying gas pressure at 85 K. The combination of the quantitative nature of the total neutron scattering technique and the modelling performed using the Empirical Potential Structure Refinement (EPSR) technique has allowed us to determine the behaviour of the absorbed fluid upon condensation within the pores with unprecedented detail. The results show that the number of oxygen molecules found inside the central core of the spherical pore of the sodalite cage does not vary as the gate-opening transition is induced. After going through the structural transition, there is a rearrangement of the molecules and the extra molecules entering the structure are instead pushed towards the window apertures in the open structure. These results help to provide a greater insight into the nature of the structural flexibility of ZIF-8 and to understand its gas sorption behaviour.

The original version of this Article contained an error in Figure 1b, where the blue '(ZIF-4-Zn)0.5 (ZIF-62)0.5 blend' data curve was omitted from the enthalpy response plot. This has now been corrected in both the PDF and HTML versions of the Article.

The layering of ionic liquids close to flat, charged interfaces has been identified previously through theoretical and some experimental measurements. Here we present evidence for oscillations in ion density ('layering') in a long chain ionic liquid (1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) near the interface with mica using two complementary approaches. Neutron reflection at the ionic liquid-mica interface is used to detect structure at a single interface, and surface force balance (SFB) measurements carried out with the same ionic liquid reveal oscillatory density in the liquid confined between two mica sheets. Our findings imply the interfacial structure is not induced by confinement alone. Structural forces between two mica surfaces extend to approximately twice the distance of the density oscillations measured at a single interface and have similar period in both cases.

The local solvation environment of uracil dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate has been studied using neutron diffraction techniques. At solvent:solute (ionic liquid:uracil) ratios of 3:1 and 2:1, little perturbation of the ion-ion correlations compared to those of the neat ionic liquid are observed. We find that solvation of the uracil is driven predominantly by the acetate anion of the solvent. While short distance correlations exist between uracil and the imidazolium cation, the geometry of these contacts suggest that they cannot be considered as hydrogen bonds, in contrast to other studies by Araújo et al. (J. M. Araújo, A. B. Pereiro, J. N. Canongia-Lopes, L. P. Rebelo, I. M. Marrucho, J. Phys. Chem. B 2013, 117, 4109-4120). Nevertheless, this combination of interactions of the solute with both the cation and anion components of the solvents helps explain the high solubility of the nucleobase in this media. In addition, favourable uracil-uracil contacts are observed, of similar magnitude to those between cation and uracil, and are also likely to aid dissolution.

Electrophoretic‐based (EP) technology is a leading option for black & white reflective display media, notably for e‐Readers. There is great future potential to extend electrophoretic and other colloidal dispersion based displays into a range of new application fields, such as digital signage, wearable displays and “smart windows”. These new applications require novel particle and fluid concepts, which present many materials design challenges; especially bright colour, image stability and ultra low power consumption. The paper will discuss the state of the art and present new materials for a range of pixel architectures.

Total neutron scattering studies on amino acid-based ionic liquids reveal significant directional interactions between anions, especially for serinate-derived ions.

The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC6H4NO2) at zinc microelectrodes in the [C4mPyrr][NTf2] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC6H4NO2 is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.

AbstractWe demonstrate the “biprimary” color system with dual particle electrophoretic dispersions and a 3‐electrode system. Preliminary contrast ratios reach 10:1. Furthermore an electrokinetic cell is demonstrated confirming basic functionality for EKD panels. A theoretical pixel simulation confirms biprimary doubles the color performance compared to RGBW pixels.

A new biprimary color system is demonstrated for single‐layer reflective displays, capturing much of the improved color performance of multilayer displays while potentially maintaining single‐layer display advantages in high resolution and faster switching. Electrophoretic pixels were operated with dual‐particle complementary‐colored dispersions such as green/magenta (G/M). Using simple interdigitated three‐electrode architecture, four colored states (KWGM) were achieved with a preliminary contrast ratio of 10 : 1. Furthermore, biprimary ink dispersions were shown to be functional in a more advanced electrokinetic pixel structure. A full‐color biprimary pixel contains three complementary subpixels (G/M, B/Y, R/C), and the requisite electrophoretic ink dispersions were also formulated and spectrally characterized in this work. Lastly, theoretical color space mapping confirms that the biprimary concept provides twice the brightness and twice the color fraction compared with the conventional RGBW subpixel approach, and that the biprimary concept can approach performance close to that of magazine print (Specifications for Web‐Offset Print).

The solid-state polymorphism of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], has been investigated via low-temperature and high-pressure crystallisation experiments. The samples have been characterised by single-crystal X-ray diffraction, optical microscopy and Raman spectroscopy. The solid-state phase behaviour of the compound is confirmed and clarified with respect to previous phase diagrams. The structures of the previously reported γ-form, which essentially exhibits a G′T cation conformation, as well as those of the elusive β- and α-forms, are reported. Crystals of the β-phase are twinned and the structure is heavily disordered; the cation conformation in this form is predominantly TT, though significant contributions from other less frequently encountered conformers are also observed at low temperature and high pressure. The cation conformation in the α-form is GT; the presence of the G′T conformer at 193 K in this phase can be eliminated on cooling to 100 K. Whilst X-ray structural data are overall in good agreement with previous interpretations based on Raman and NMR studies, they also reveal a more subtle interplay of intermolecular interactions, which give rise to a wider range of conformers than previously considered.

Radical anions of 1-bromo-4-nitrobenzene (p-BrC6H4NO2) are shown to be reactive in the room temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, ([C(4)mPyrr][NTf2]), by means of voltammetric measurements. In particular, they are shown to react via a DISP type mechanism such that the electrolysis of p-BrC6H4NO2 occurs consuming between one and two electrons per reactant molecule, leading to the formation of the nitrobenzene radical anion and bromide ions. This behaviour is a stark contrast to that in conventional non-aqueous solvents such as acetonitrile, dimethyl sulfoxide or N,N-dimethylformamide, which suggests that the ionic solvent promotes the reactivity of the radical anion, probably via stabilisation of the charged products.

The electrochemical reduction of benzoic acid in the presence and absence of hydrogen (H(2)) has been investigated using a 10 μm diameter platinum microelectrode in four different room temperature ionic liquids (RTILs), namely [C(4)mim][NTf(2)], [C(4)mpyrr][NTf(2)], [C(4)mim][OTf] and [C(4)mim][BF(4)], versus Ag/Ag(+). In all cases, reductive voltammetry is observed, and is suggested to occur via a CE mechanism in which dissociation of benzoic acid is followed by electron transfer to H(+) ultimately forming adsorbed hydrogen. Furthermore, the adsorbed H atoms, formed from the reduction of benzoic acid, could be used to achieve the rapid hydrogenolysis of the organic compound (bis(benzyloxycarbonyl)-l-lysine) on the timescale of the voltammetric technique under moderate conditions (25 °C).

A series of phosphorodiamidite reagents have been readily prepared using bis{(trifluoromethyl) sulfonyl} imide based ionic liquids and compared with their syntheses in conventional organic solvents. This method demonstrates a versatile procedure that allows access to both known and novel phosphorodiamidite reagents, whilst addressing issues such as moisture sensitivity and product selectivity present in current molecular based protocols. This method negates the need for reagent purification, whilst allowing for the reactions to be conducted at high concentrations.

The electrode potentials for the two one electron oxidations of 1,2-diferrocenylethylene (bisferrocene, BF) were studied relative to that of the one electrode oxidation of decamethylferrocene in a variety of RTILs. The difference in these potentials was found to be very sensitive to the anion component of the ionic liquid showing the scope of these solutes as 'designer media' to tune the thermodynamic properties of solutes dissolved in them.

A range of nucleoside phosphoramidites incorporating small amino substituents have been readily synthesised using ionic liquid stabilised phosphorodiamidites coupled with mechanochemistry.