The effect of the anion on the physical properties of trihalide-based N,N-dialkylimidazolium ionic liquids

Low viscosity, high density trihalide-based 1-n-butyl-3-methylimidazolium ionic liquids have been prepared and characterised. Key physical properties (density, conductivity, melting point, refractive index, surface tension and diffusion coefficient) of the ionic liquids have been determined and are compared with those of other 1,3-dialkylimidazolium molten salts. The relationship between anion identity and the physical properties of the ionic liquids under investigation is discussed.     

Fast,Facile and Solvent-Free Dry-Melt Synthesis of Oxovanadium(IV) Complexes: Simple Design with High Potency towards Cancerous Cells

A range of oxobis(phenyl-1,3-butanedione) vanadium(IV) complexes have been successfully synthesized from cheap starting materials and a simple and solvent-free one-pot dry-melt reaction. This direct, straightforward, fast and alternative approach to inorganic synthesis has the potential for a wide range of applications. Analytical studies confirm their successful synthesis, purity and solid-state coordination, and we report the use of such complexes as potential drug candidates for the treatment of cancer. After a 24 hour incubation of A549 lung carcinoma cells with the compounds, they reveal cytotoxicity values elevenfold greater than cisplatin and remain non-toxic towards normal cell types. Additionally, the complexes are stable over a range of physiological pH values and show the potential for interactions with bovine serum albumin.     

A tale of hydrogen abstraction,initially detected via X‐ray diffraction

Reaction of a bis‐tetrazinyl pyridine pincer ligand, btzp, with a vanadium(III) reagent gives not a simple adduct but dichlorido{3‐methyl‐6‐[6‐(6‐methyl‐1,2,4,5‐tetrazin‐3‐yl‐κN²)pyridin‐2‐yl‐κN]‐1,4‐dihydro‐1,2,4,5‐tetrazin‐1‐yl‐κN¹}oxidovanadium(IV) acetonitrile 2.5‐solvate, [V(C₁₁H₁₀N₉)Cl₂O]·2.5CH₃CN, a species which X‐ray diffraction reveals to have one H atom added to one of the two tetrazinyl rings. This H atom was first revealed by a short intermolecular N...Cl contact in the unit cell and subsequently established, from difference maps, to be associated with a hydrogen bond. One chloride ligand has also been replaced by an oxide ligand in this synthetic reaction. This formula for the complex, [V(Hbtzp)Cl₂O], leaves open the question of both ligand oxidation state and spin state. A computational study of all isomeric locations of the H atom shows the similarity of their energies, which is subject to perturbation by intermolecular hydrogen bonding found in X‐ray work on the solid state. These density functional calculations reveal that the isomer with the H atom located as found in the solid state contains a neutral radical Hbtzp ligand and tetravalent d¹ V center, but that these two unpaired electrons are more stable as an open‐shell singlet and hence antiferromagnetically coupled.     

Quantum magnetism in the paratacamite family: towards an ideal kagomé lattice

We report muon spin rotation measurements on the S=1/2 (Cu2+) paratacamite ZnxCu4-x(OH)6Cl2 family. Despite a Weiss temperature of approximately -300 K, the x=1 compound is found to have no transition to a magnetic frozen state down to 50 mK as theoretically expected for the kagomé Heisenberg antiferromagnet. We find that the limit between a dynamical and a partly frozen ground state occurs around x=0.5. For x=1, we discuss the relevance to a singlet picture.     

Memory effect of mobile phase additives in chiral separations on a Chiralpak AD column

Using chiral probes shown to be sensitive to the presence of mobile phase additives, a memory effect for these additives by an amylosic column was demonstrated. Exposure to these additives gave prolonged chromatographic performance changes even after their removal from the mobile phase. This finding is consistent with strong binding of the additives to the stationary phase. A procedure to remove bound additives was developed.