Magnetic Anisotropy in “Scorpionate” First‐Row Transition‐Metal Complexes: A Theoretical Investigation

In this work we have analyzed in detail the magnetic anisotropy in a series of hydrotris(pyrazolyl)borate (Tp^?) metal complexes, namely [VTpCl]⁺, [CrTpCl]⁺, [MnTpCl]⁺, [FeTpCl], [CoTpCl], and [NiTpCl], and their substituted methyl and tert‐butyl analogues with the goal of observing the effect of the ligand field on the magnetic properties. In the [VTpCl]⁺, [CrTpCl]⁺, [CoTpCl], and [NiTpCl] complexes, the magnetic anisotropy arises as a consequence of out‐of‐state spin–orbit coupling, and covalent changes induced by the substitution of hydrogen atoms on the pyrazolyl rings does not lead to drastic changes in the magnetic anisotropy. On the other hand, much larger magnetic anisotropies were predicted in complexes displaying a degenerate ground state, namely [MnTpCl]⁺ and [FeTpCl], due to in‐state spin–orbit coupling. The anisotropy in these systems was shown to be very sensitive to perturbations, for example, chemical substitution and distortions due to the Jahn–Teller effect. We found that by substituting the hydrogen atoms in [MnTpCl]⁺ and [FeTpCl] by methyl and tert‐butyl groups, certain covalent contributions to the magnetic anisotropy energy (MAE) could be controlled, thereby achieving higher values. Moreover, we showed that the selection of ion has important consequences for the symmetry of the ground spin–orbit term, opening the possibility of achieving zero magnetic tunneling even in non‐Kramers ions. We have also shown that substitution may also contribute to a quenching of the Jahn–Teller effect, which could significantly reduce the magnetic anisotropy of the complexes studied.     

Synthesis of indene derivatives via reactions of vinylidenecyclopropanes with the N-acyliminium cations generated from hydroxylactams

A novel route for the synthesis of 1H-indene derivatives via the reactions of vinylidenecyclopropanes (VCPs) with the N-acyliminium cations generated from hydroxylactams is described.     

Bifurcations in basic models of delayed force control

Nonlinear Dynamics - Basic single-degree-of-freedom mechanical models of force control are presented to achieve desired contact forces between actuators and objects. Nonlinear governing equations...     

Stereoselective cycloaddition of diphenylisobenzofuran to N-arylitaconimides

A reaction of 1,3-diphenylisobenzofuran with N-arylitaconimides gives the [4+2] cycloaddition products with the 11′-oxaspiro[pyrrolidine-3,9′-tricyclo[6.2.1.0 ^2,7 ]undeca-2′,4′,6′-triene-2,5-dione] skeleton as a single diastereomer.     

Novel Template Sorbents for Separation of Americium(III) from Nitric Acid Solutions: Search of Optimal Ion‐Imitator of AmIII

A series of new template sorbents that enable selective and effective sorption of Am^III from 0.5 to 4M HNO₃ solutions containing high concentrations of Fe^III and Zr^IV was synthesized from (ethenyl)(diphenyl)phosphine oxide. La^III, Ce^III, and Pr^III were used as template elements imitating the properties of Am^III. The highest efficiency of separation of Am^III from high amounts of Fe^III and Zr^IV was displayed by the Ce^III‐based sorbent.     

Delay-induced bifurcations in collocated position control of an elastic arm

The interference of the elasticity of a single robotic arm and the unavoidable time delay of its position control is analysed from nonlinear vibrations viewpoint. The simplified mechanical model of two blocks and a connecting spring considers the first vibration mode of the arm, while the collocated proportional-derivative (PD) control uses the state of the first block only and actuates also there. It is assumed that the relevant nonlinearity is the saturation of the delayed control force. The linear stability analysis proves that stabilizable and non-stabilizable parameter regions follow each other periodically even for large spring stiffnesses and for tiny time delays. Hopf bifurcation calculation is carried out after an infinite-dimensional centre manifold reduction, and closed-form algebraic expressions are given for the amplitudes of the emerging oscillations. These results support the experimental tuning of the control gains since the parameters of the arising and often unexpected self-excited vibrations can serve as a guide for this practical procedure.

     

Structural and optical characterization of colloidal Se nanoparticles prepared via the acidic decomposition of sodium selenosulfate

Colloidal selenium nanoparticles (NPs) were synthesized via acidic decomposition of sodium selenosulfate. The effects of synthesis and post-synthesis treatment conditions on the size, structure and size distribution of the Se nanoparticles are discussed. It is shown that the decomposition of sodium selenosulfate with non-oxidative acids (e.g., HCl) in aqueous solutions of polymers (sodium polyphosphate, gelatin, polyvinyl alcohol, polyethyleneglycole) and surfactants (sodium dodecylsulfonate, cetylpyridinium chloride) results in the formation of amorphous 25–200 nm Se nanoparticles converting upon ageing at 90 °C into trigonal 150–250 nm Se nanocrystals. Optical properties (absorption and Raman spectra) of freshly prepared and aged Se nanoparticles both in colloidal solutions and in polymeric (polyvinyl alcohol) films are analyzed.