Magnetic Anisotropy of Cyanide‐Bridged Core and Core–Shell Coordination Nanoparticles Probed by X‐ray Magnetic Circular Dichroism

The local symmetry and local magnetic properties of 6 nm‐sized, bimetallic, cyanide‐bridged CsNiCr(CN)₆ coordination nanoparticles 1 and 8 nm‐sized, trimetallic, CsNiCr(CN)₆@CsCoCr(CN)₆ core–shell nanoparticles 2 were studied by X‐ray absorption spectroscopy (XAS) and X‐ray magnetic circular dichroism (XMCD). The measurements were performed at the Ni^II, Co^II, and Cr^III L_2,3 edges. This study revealed the presence of distorted Ni^II sites located on the particle surface of 1 that account for the uniaxial magnetic anisotropy observed by SQUID measurements. For the core–shell particles, a combination of the exchange anisotropy between the core and the shell and the pronounced anisotropy of the Co^II ions is the origin of the large increase in coercive field from 120 to 890 Oe on going from 1 to 2 . In addition, XMCD allows the relative orientation of the magnetic moments throughout the core–shell particles to be determined. While for the bimetallic particles of 1 , alignment of the magnetic moments of Cr^III ions with those of Ni^II ions leads to uniform magnetization, in the core–shell particles 2 the magnetic moments of the isotropic Cr^III follow those of Co^II ions in the shell and those of Ni^II ions in the core, and this leads to nonuniform magnetization in the whole nanoobject, mainly due to the large difference in local anisotropy between the Co^II ions belonging to the surface and the Ni^II ions in the core.     

Mononuclear and heterobimetallic palladium(II) and platinum(II) complexes containing the mixed ligands <Emphasis Type="Italic">N</Emphasis>-(2-pyridyl or 2-pyrimidyl) acetamide and tertiary diphosphine

Palladium(II) and platinum(II) complexes containing mixed ligands N-(2-pyridyl)acetamide (AH) or N-(2-pyrimidyl)acetamide (BH) and the diphosphines Ph₂P(CH₂) _n PPh₂, (n = 1, 2 or 3) have been prepared. The prepared complexes [Pd(A)₂(diphos)] or [Pd(B)₂(diphos)] have been used effectively to prepare bimetallic complexes of the type [(diphos)Pd(μ-L)₂M′Cl₂] where M′ = Co, Cu, Mn, Ni, Pd, Pt or SnCl₂; L = A or B. The prepared complexes were characterized by elemental analysis magnetic susceptibility, i.r. and UV–Vis spectral data. ³¹P–{¹H}-n.m.r. data have been applied to characterize the produced linkage isomers.     

Selective pyrolysis of bifunctional compounds: gas-phase elimination of carbonate-ester functionalities

Compounds containing both carbonate and ester functionalities were synthesized and then subjected to online-GC gas-phase pyrolysis. The carbonate groups were cleaved selectively in all elimination reactions. The end products of the reaction were found to be affected by the nature of the substrate. The presence of hydrogen and carbonyl substituents on the carbon β to the carbonate group resulted in further product decomposition through a concerted six-membered transition state. Results from flash vacuum pyrolysis (FVP) and analysis of the GC data indicate that the cleavage of the carbonate group is fast, and that the slower secondary decomposition reactions are independent of the presence of the carbonate group. Spectroscopic analyses of the products are reported.     

A novel undecametallic iron(III) cluster with an S = (11)/(2) spin ground state

The reaction of [NEt(4)](2)[Fe(2)OCl(6)] with sodium benzoate, 4,6-dimethyl-2-hydroxypyrimidine (dmhp), and 1,1,1-tris(hydroxymethyl)ethane (H(3)thme) gives the undecametallic compound [NEt(4)][Fe(11)O(4)(O(2)CPh)(10)(thme)(4)(dmhp)(2)Cl(4)]. X-ray crystallography, EPR spectroscopy, bulk magnetic susceptibility studies, and low-temperature single-crystal magnetic measurements were used to characterize the compound. Magnetic measurements indicate an S = (11)/(2) ground state with the parameters g = 2.03 and D = -0.46 cm(-)(1). Single-crystal magnetic studies show hysteresis of molecular origin at T < 1.2 K with fast quantum mechanical tunneling at zero field.     

Grafting a monolayer of superparamagnetic cyanide-bridged coordination nanoparticles on Si(100)

The grafting of a monolayer of 6 nm superparamagnetic cyanide-bridged CsNiCr nanoparticles was achieved on a Ni(II)-functionalized Si(100) substrate; magnetic studies reveals that the grafted nanoparticles are nearly magnetically isolated within the monolayer.     

Photomagnetic nanorods of the Mo(CN)8Cu2 coordination network

Nanorods of the photomagnetic coordination network Mo(CN)8Cu2 coated with polyvinylpyrrolidone were prepared and exhibit an enhanced effect upon irradiation when compared to the bulk.     

Single‐Molecule Magnet Behavior of Individual Polyoxometalate Molecules Incorporated within Biopolymer or Metal–Organic Framework Matrices

The chemically and structurally highly stable polyoxometalate (POM) single‐molecule magnet (SMM) [(FeW₉O₃₄)₂Fe₄(H₂O)₂]^10? (Fe₆W₁₈) has been incorporated by direct or post‐synthetic approaches into a biopolymer gelatin (Gel) matrix and two crystalline metal–organic frameworks (MOFs), including one diamagnetic (UiO‐67) and one magnetic (MIL‐101(Cr)). Integrity of the POM in the Fe₆W₁₈@Gel, Fe₆W₁₈@UiO‐67 and Fe₆W₁₈@MIL‐101(Cr) composites was confirmed by a set of complementary techniques. Magnetic studies indicate that the POMs are magnetically well isolated. Remarkably, in Fe₆W₁₈@Gel, the SMM properties of the embedded molecules are close to those of the crystals, with clear quantum tunneling steps in the hysteresis loops. For the Fe₆W₁₈@UiO‐67 composite, the molecules retain their SMM properties, the energy barrier being slightly reduced in comparison to the crystalline material and the molecules exhibiting a tunneling rate of magnetization significantly faster than for Fe₆W₁₈@Gel. When Fe₆W₁₈ is introduced into MIL‐101(Cr), the width of the hysteresis loops is drastically reduced and the quantum tunneling steps are smeared out because of the magnetic interactions between the antiferromagnetic matrix and the SMM guest molecules.     

Onset of entrainment and degree of dispersion in dual continuous horizontal oil–water flows

The transition from stratified to dual continuous oil–water flow (where each phase retains its continuity but there is dispersion of one phase into the other) as well as the dispersed phase fractions in the layers of the dual continuous pattern, were studied experimentally. Transition to this pattern from stratified flow occurs when drops of one phase appear into the other (onset of entrainment). The studies were carried out in a 38 mm ID horizontal stainless steel test section using two different inlet geometries, a T- and a Y-junction. The patterns were visualized through a transparent acrylic section located at 7 m from the inlet using a high speed video camera. Phase distribution measurements in a pipe cross section were obtained just before the acrylic section with a local impedance probe and the results were used to calculate the volume fraction of each phase entrained into the other. The onset of entrainment was found to occur at lower superficial water velocities as the oil superficial velocities increased. However, the inlet geometry did not affect significantly the transition line. During dual continuous flow, the dispersion of one phase into the opposite was found to extend further away from the interface with increasing water superficial velocity for a certain oil superficial velocity. An increase in the superficial water velocity increased the entrained fraction of water in oil (E_w/o) but there was no trend with the oil velocity. Similarly, an increase in the superficial oil velocity increased the fraction of oil drops in water (E_o/w) but the water velocity had no clear effect. The entrainment fractions were affected by the inlet geometry, with the T-inlet resulting in higher entrainment than the Y-inlet, perhaps because of the increased mixing induced by the T-inlet. The difference between the two inlets increased as the oil and water velocities increased.