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Ionic liquids containing lanthanide halide anions give the opportunity to investigate magnetic behaviour in non-ordered systems. Reported herein is the synthesis and characterization of ionic liquids containing a series of lanthanide halide anions, with the resulting materials displaying unusual behaviour below 50 K. Specifically, the ionic liquid structural glass formation appears to drive magnetic behaviour due to cluster formation of the anions during rapid cooling. This system presents a possible probe to study the dynamics of glass forming materials.

Antiseptic agents are the primary arsenal to disinfect skin and prevent pathogens spreading within the host as well as into the surroundings; however the Food and Drug Administration published a report in 2015 requiring additional validation of nearly all current antiseptic agents before their continued use can be allowed. This vulnerable position calls for urgent identification of novel antiseptic agents. Recently, the ability of a deep eutectic, Choline And Geranate (CAGE), to treat biofilms of Pseudomonas aeruginosa and Salmonella enterica was demonstrated. Here it is reported that CAGE exhibits broad-spectrum antimicrobial activity against a number of drug-resistant bacteria, fungi, and viruses including clinical isolates of Mycobacterium tuberculosis, Staphylococcus aureus, and Candida albicans as well as laboratory strains of Herpes Simplex Virus. Studies in human keratinocytes and mice show that CAGE affords negligible local or systemic toxicity, and an ≈180-14 000-fold improved efficacy/toxicity ratio over currently used antiseptic agents. Further, CAGE penetrates deep into the dermis and treats pathogens located in deep skin layers as confirmed by the ability of CAGE in vivo to treat Propionibacterium acnes infection. In combination, the results clearly demonstrate CAGE holds promise as a transformative platform antiseptic agent for preventive as well as therapeutic applications.

Room temperature ionic liquids, or RTILs, based on tetraalkylphosphonium (PR(4)(+)) cations were used as the basis of a platform that enables separation of dyes from textiles, extraction of dyes from aqueous solution, and identification of the dyes by MALDI-MS in a single experimental step for forensic purposes. Ionic liquids were formed with PR(4)(+) cations and ferulate (FA), α-cyano-4-hydroxycinnamate (CHCA), and 2,5-dihydroxybenzoate (DHB) anions. The use of tetraalkylphosphonium-based ionic liquids in MALDI-MS allowed detection of small molecule dyes without addition of a traditional solid MALDI matrix.

A novel class of scintillating materials, which are nanocomposites of known scintillators, is described. These nanocomposite materials are expected to have improved properties with respect to the properties of the bulk scintillators from which they are derived. Improvements include enhanced light output, reduced cost and greater size scalability. Optical properties of the nanocomposite phosphor components are described, with emphasis on the origin of the enhanced light yield. Finally, results from our first nanocomposite scintillator, including photopeak measurements, are described. The photopeak measurements demonstrate the proof-of-principle of the nanocomposite scintillator concept.

The Raman and infrared spectra of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids ([C2-4MIM][BF4]) are reported and analyzed using Density Functional Theory (DFT) and RHF methods at the 6-311+G(2d,p) computational level. The B3LYP (DFT) and RHF calculations reproduce the vibrational spectra of 1-ethyl-3-methyl imidazolium tetrafluoroborate [EMIM][BF4], 1-propyl-3-methyl imidazolium tetrafluoroborate [PMIM][BF4] and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF4] using correction factors of 0.963–0.967 (DFT) and 0.913–0.916 (RHF) with correlation coefficients R2 of 0.999 using the fully optimized structures. Theoretical (DFT) alkyl side chain conformational changes in the 1-alkyl-3-methyl tetrafluoroborate ionic liquids have only a limited effect on the theoretical gas phase vibrations. The gas phase molecular structures of the [C2–4MIM][BF4] ion pairs suggest hydrogen bonding interactions between the fluorine atoms of the BF4− anion and the C2 hydrogen on the imidazolium ring. Additional interactions are observed between [BF4] and H atoms on the adjacent alkyl side chains in all polymorphic structures.

Ionic liquids are salts that are liquid at or near room temperature. Their wide liquid range, good thermal stability, and very low vapor pressure make them attractive for numerous applications. The general approach to creating ionic liquids is to employ a large, unreactive, low symmetry cation with and an anion that largely controls the physical and chemical properties. The most common cations used in ionic liquids are N-alkylpyridinium and N,N′-dialkylimidazolium. Another very effective cation for the creation of ionic liquids is tetraalkylphosphonium, [PR1R2R3R4]+. The alkyl groups, Rn, generally are large and not all the same. The halide salts of several phosphonium cations are available as starting materials for metathesis reactions used to prepare ionic liquids. The large phosphonium cations can combine with relatively large anions to make viscous but free flowing liquids with formula mass greater than 1000 g mol−1. Some other more massive salts are waxes and glasses. The synthesis and the physical, chemical, and optical properties of phosphonium-ionic liquids having anions with a wide range of masses were measured and are reported here.

The crystal structures and magnetic properties of the nitronyl nitroxide radicals 4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H-imidazol-1-yloxyl) (1), 4,5-dihydro-2,4,4,5,5-pentamethyl-3-oxido(1H-imidazol-1-yloxyl) (2), 2-(4-chlorophenyl)-4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H-imidazol-1-yloxyl) (3), and 4,5-dihydro-2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-3-oxido(1H-imidazol-1-yloxyl) (4) are reported. Compound 1 has two polymorphic forms: the α phase is monoclinic (P21/n space group), with a single molecule in the asymmetric unit, and the β phase is monoclinic (P21/c space group), with four molecules in the asymmetric unit. In the two polymorphs, the molecules are arranged in dimers formed by hydrogen bonds of the type CH⋅⋅⋅ON. The crystal structure of 3 contains layers of antiparallel ribbons of molecules. Compound 4 crystallizes with solvent molecules, and an intramolecular hydrogen bond is formed between the 2-OH group of the phenyl ring and the nitroxide O-atom. Compound 4 also loses the two O-atoms of the nitroxide moiety upon heating to 90°. Magnetic measurements showed that both α and β polymorphs of 1 exhibit antiferromagnetic coupling. The best fit to the experimental data was obtained using BleanyBower's singlet-triplet model (H=−2JSaSb): J=−11.2 K for the α phase and J=−15.0 K for the β phase. Compounds 3 and 4 show no evidence for spin coupling.

By using the tripodal tetradentate ligand tris(2-benzimidazolylmethyl)amine (H(3)ntb), which can have several charge states depending on the number of secondary amine protons, mononuclear octahedral and dinuclear trigonal bipyramidal Fe(III) complexes were prepared. The reaction of mononuclear octahedral [Fe(III)(H(3)ntb)Cl(2)]ClO(4), 1, with 3 equiv of sec-butylamine in methanol led to the formation of mononuclear cis-dimethoxo octahedral Fe(III)(H(2)ntb)(OMe)(2), 2. One equivalent of the sec-butylamine was used to generate the monoanionic H(2)ntb(-) ligand where one of the three amines in the benzimidazolyl groups was deprotonated. The remaining 2 equiv were used to generate two methoxides that were coordinated to the octahedral Fe(III) ion in a cis fashion as demonstrated by the chlorides in 1. Reaction of 1 with excess (7 equiv) sec-butylamine generated the doubly deprotonated dianionic Hntb(2-) that stabilized the dinuclear mu-oxo Fe(III)(2)O(Hntb)(2), 3, adopting a five-coordinate trigonal bipyramidal geometry. The magnetic data for 3 are consistent with the antiferromagnetically coupled Fe(III) (S = 5/2) sites with the coupling constant J = -127 cm(-1).

Ionic liquids, with their vast applications, have been touted as being thermally stable to very high temperatures. However, decomposition not detected by standard TGA and NMR techniques are observed with spectroscopic techniques sensitive enough to see small amounts of impurities. Decomposition temperatures of common ionic liquids appear to occur at hundreds of degrees below those temperatures previously reported.

The reaction of [Et4N]I and tetracyanoethylene (TCNE) forms [Et4N]2[TCNE]2, which possesses [TCNE]22− with a 2.827(3) A intradimer CC bond distance and exhibits νCN at 2191, 2170 and 2163 cm−1, νCC at 1365 cm−1, and UV-Vis bands at 26 150 and 16 850 cm−1.

An intriguing and novel charge-transfer complex between dimethyldihydrophenazine and diethylviologen has been crystallized from an ionic liquid at room temperature, resulting in an interesting stacking motif of interrupted D***A***D type triads: efficient formation of the complex is seen within an ionic liquid and acetone, with the complex absorbing strongly across nearly the entire visible-NIR spectral region.

Three groups of singlet ground state [TCNE](2) (2-) (TCNE=tetracyanoethylene) dimers with characteristic intradimer CC separations (r) and dihedral angles (d) [i.e., group S(t) (r approximately 1.6 A; d=180 degrees ), L(t) (r approximately 3.5 A; d=180 degrees ), and L(c) (r approximately 2.9 A; d= approximately 0 degrees ); notation: S/L: short/long bond length; subscript t/c: trans/cis, respectively] are experimentally characterized. The S(t) group is comprised of sigma-dimers of [TCNE](.-) and octacyanobutanediide, [C(4)(CN)(8)](2-), which have a typical, albeit long, sp(3)-sp(3) sigma bond (r approximately 1.6 A) between each [TCNE](.-) moiety and characteristic nu(CN), nu(CC), and delta(CCN) IR absorptions. The L groups are structurally characterized as pi-dimers of [TCNE](.-) that are either eclipsed with r approximately 2.9 A (L(c)) and the nitriles bend away from the nominal TCNE plane away from the center of the dimer by 5.0 degrees (approximately sp(2.17)) or are noneclipsed with r approximately 3.5 A (L(t)) and the nitriles bend toward the center of the dimer by 1.9 degrees ( approximately sp(2.06)). Ab initio computations on isolated dimers were used to study the formation and stability of these exceptionally long CC (or =2.9 A) bonding interactions as well as the process of pi-[TCNE](2) (2-) dimer formation for the L(c) and L(t) groups. The results of these computational studies show that the ground-state potential curve is that of a closed-shell/open-shell singlet, depending on the distance. The short S(t) group (r approximately 1.6 A) of dimers in this surface are true minimum-energy structures; however, the L(t) and L(c) groups are unstable, although two different nonphysical minima are found when imposing a double occupancy of the orbitals. These minima are metastable relative to dissociation into the isolated [TCNE](.-) units. Consequently, the existence of dimer dianions in crystals is due to cation.[TCNE](-) interactions, which provide the electrostatic stabilization necessary to overcome the intradimer electrostatic repulsion. This cation-mediated pi*-pi* [TCNE](-).[TCNE](-) interaction complies with Pauling's definition of a chemical bond. This bonding interaction involves the pi* orbitals of each fragment, and arise from the overlap of the b(2g) SOMO on each of the two [TCNE](.-)s to form a filled b(2u) [TCNE](2) (2-) orbital. Although a pi dimer typically forms, if the fragments are close enough a sigma dimer can form. Due to the presence of cation-mediated intradimer CC bonding interactions the L(c) group of pi-[TCNE](2) (2-) dimers exhibits experimentally observable nu(CN) IR absorptions at 2191+/-2 (m), 2173+/-3 (s), and 2162+/-3 cm(-1) (s) and nu(CC) at 1364+/-3 cm(-1) (s) as well as a new UV-Vis feature in the range of 15 000 to 18 200 cm(-1) (549 to 667 nm) and averaging 16 825+/-1180 cm(-1) (594 nm) assigned to the predicted new intradimer (1)A(1g) --(1)B(1u) transition and is purple on reflected light. Upon cooling to 77 K in 2-methyl tetrahydrofuran, this new band occurs at 18 940 cm(-1) (528 nm) for [[Et(4)N](+)](2)[TCNE](2) (2-), and the yellow solution turns deep red. Group L(t) is characterized by nu(CN) absorptions at 2215+/-2, 2197+/-3, and 2180+/-4 cm(-1) and nu(CC) at 1209+/-9 cm(-1) (w), while group S(T) has nu(CN) bands at 2215+/-4, 2157+/-3, and 2107+/-4 cm(-1) and nu(CC) at 1385+/-1 cm(-1) (vs).

Ionic liquids are being employed in almost all areas of chemistry and materials, yet there are inherent issues which arise if the utmost care is not taken in the preparation and purification of these materials. They are not easily synthesized and purified using the existing methods. We describe a reliable method for producing large quantities of high quality ionic liquids. Additionally, we show that imidazoliums are not ‘special’ due to their ‘inherently fluorescent’ nature, that spectroscopically clean imidazoliums are attainable, and most classes of ionic liquids do exhibit fluorescent backgrounds when extreme care is not taken during their synthesis and purification.

The cover picture shows the b2g HOMO for [TCNE].−, the structure (top, middle) and bonding of the π-[TCNE]22− dimer and its b2u HOMO and b1g LUMO. At the bottom of the picture solutions of [Et4N]2[TCNE]2 in dichloromethane solution at room temperature, which is yellow due to the presence of [TCNE].−, and at −90 °C, which is red due to shifting of the 2 [TCNE].− ⇌ [TCNE]22− equilibrium to the right, thus forming [TCNE]22− in solution. For more details see the article by J. S. Miller et al. on p. 4894 ff.