Anion control of isomerism, crystal packing and binding properties in a mononuclear zinc complex

The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H₂O)(NO₃)](NO₃) (1), and [Zn(DDOP)(H₂O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode.     

Positive ion pair cooperativity exhibited for the binding of phosphate under physiological conditions

The synthesis of a heteroditopic receptor which exhibits positive cooperativity for the binding of phosphate ion pairs under physiological conditions. Optimised complementarity between crown ether host and metal guest leads to increased binding affinity, Ka.     

Novel coordination polymers and structural systematics in the hydrothermal M,M' trans-3(-3-pyridyl)acrylic acid system

The bifunctional ligand trans-3-(3-pyridyl)acrylic acid has been utilized to promote the formation of a novel hetero-metallic [Cu3(C8H6NO2)6Nd2(NO3)6] (1) and two homometallic: [Nd(C8H6NO2)3H2O] (2) and [Cu(C8H6NO2)2] x H2O (3) metal organic framework (MOF) materials. The philosophy here is that a mixture of hard (Nd3+) and softer metal cations will show preference for the carboxylic and pyridyl functional groups, respectively. As such, a 3-D topology 1 has emerged as a stable, heterometallic structure. Efforts to explore structural systematics in this system have led to the synthesis of homometallic end members and hence the formation of a 2-D coordination polymer 2, and a 1-D coordination polymer 3. Presented is an analysis of the effect of a second metal centre on coordination environment, overall structure formation, thermal and luminescence properties.     

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Magnetoresistance in point contacts of the Heusler alloy Co2Cr0.6Fe0.4Al

Following a recent report predicting half-metallicity of Co₂Cr_0.6Fe_0.4Al, we have examined point contacts of this material. Large magnetoresistances (up to 80%) have been observed at room temperature in small fields (10 mT). Magnetostriction in these fields is negligible. A spin polarisation of 81% is inferred. Mössbauer spectra show that 90% of the iron is ordered. The magnetisation of the alloy is 3.65μ_B per formula unit, and its Curie temperature is 665 K.     

Dielectric constant and microwave conductivity of the vanadium bronze Na0.33V2O5

Measurements of the dielectric constant and microwave conductivity are reported for the vanadium bronze Na_0.33V₂O₅. The dielectric constant is highly anisotropic and very large parallel to the highly conducting direction, while the conductivity is strongly dispersive. The results can be consistently interpreted by considering Na_0.33V₂O₅ as a quasi-one-dimensional conductor in which, at low temperatures, a pseudo-gap opens in the open-electron density of states due to inter-site correlations.