Square‐Planar Ruthenium(II) Complexes: Control of Spin State by Pincer Ligand Functionalization

Functionalization of the PNP pincer ligand backbone allows for a comparison of the dialkyl amido, vinyl alkyl amido, and divinyl amido ruthenium(II) pincer complex series [RuCl{N(CH₂CH₂PtBu₂)₂}], [RuCl{N(CHCHPtBu₂)(CH₂CH₂PtBu₂)}], and [RuCl{N(CHCHPtBu₂)₂}], in which the ruthenium(II) ions are in the extremely rare square‐planar coordination geometry. Whereas the dialkylamido complex adopts an electronic singlet (S=0) ground state and energetically low‐lying triplet (S=1) state, the vinyl alkyl amido and the divinyl amido complexes exhibit unusual triplet (S=1) ground states as confirmed by experimental and computational examination. However, essentially non‐magnetic ground states arise for the two intermediate‐spin complexes owing to unusually large zero‐field splitting (D>+200 cm^?1). The change in ground state electronic configuration is attributed to tailored pincer ligand‐to‐metal π‐donation within the PNP ligand series.     

Flow due to a plate that applies an accelerated shear to a second grade fluid between two parallel walls perpendicular to the plate

The velocity field and the shear stresses corresponding to the motion of a second grade fluid between two side walls, induced by an infinite plate that applies an accelerated shear stress to the fluid, are determined by means of the integral transforms. The obtained solutions, presented under integral form in term of the solutions corresponding to the flow due to a constant shear on the boundary, satisfy all imposed initial and boundary conditions. In the absence of the side walls, they reduce to the similar solutions over an infinite plate. The Newtonian solutions are obtained as limiting cases of the general solutions. The influence of the side walls on the fluid motion as well as a comparison between the two models is shown by graphical illustrations.     

The Rayleigh–Stokes problem for an edge in a generalized Oldroyd-B fluid

The velocity field corresponding to the Rayleigh–Stokes problem for an edge, in an incompressible generalized Oldroyd-B fluid has been established by means of the double Fourier sine and Laplace transforms. The fractional calculus approach is used in the constitutive relationship of the fluid model. The obtained solution, written in terms of the generalized G-functions, is presented as a sum of the Newtonian solution and the corresponding non-Newtonian contribution. The solution for generalized Maxwell fluids, as well as those for ordinary Maxwell and Oldroyd-B fluids, performing the same motion, is obtained as a limiting case of the present solution. This solution can be also specialized to give the similar solution for generalized second grade fluids. However, for simplicity, a new and simpler exact solution is established for these fluids. For β → 1, this last solution reduces to a previous solution obtained by a different technique.     

Flow of a viscoelastic fluid with the fractional Maxwell model between two side walls perpendicular to a plate

The unsteady flow of a viscoelastic fluid with the fractional Maxwell model between two side walls perpendicular to a plate is investigated. Exact solutions for the velocity field are established by means of the Fourier and Laplace transforms. The similar solutions for Maxwell and Newtonian fluids can be obtained as limiting cases of our results. In the absence of side walls, all solutions that have been determined reduce to those corresponding to the motion over an infinite plate.     

Flow of a generalized Maxwell fluid induced by a constantly accelerating plate between two side walls

The unsteady flow of a viscoelastic fluid with the fractional Maxwell model, induced by a constantly accelerating plate between two side walls perpendicular to the plate, is investigated by means of the integral transforms. Exact solutions for the velocity field are presented under integral and series forms in terms of the derivatives of generalized Mittag–Leffler functions. The corresponding solutions for Maxwell fluids are obtained as limiting cases for β → 1. In the absence of the side walls, all solutions that have been determined reduce to those corresponding to the motion over an infinite plate.      

Analytical and semi-analytical solutions to flows of two immiscible Maxwell fluids between moving plates

Unsteady flows of two immiscible Maxwell fluids in a rectangular channel bounded by two moving parallel plates are studied. The fluid motion is generated by a time-dependent pressure gradient and by the translational motions of the channel walls in their planes. Analytical solutions for velocity and shear stress fields have been obtained by using the Laplace transform coupled with the finite sine-Fourier transform. These analytical solutions are new in the literature and the method developed in this paper can be generalized to unsteady flows of n-layers of immiscible fluids. By using the Laplace transform and classical method for ordinary differential equations, the second form of the Laplace transforms of velocity and shear stress are determined. For the numerical Laplace inversion, two accuracy numerical algorithms, namely the Talbot algorithm and the improved Talbot algorithm are used.     

Optical spectra in the region of exciton resonances in quantum wells and quantum dots of In0.3Ga0.7As/GaAs heterostructures

The transparency, reflection and luminescence spectra of In_0.3Ga_0.7As structures with 8 nm thickness and quantum wells limited by the barrier layer GaAs of a 9 nm (upper layer) and 100 nm (bottom layer) thickness had been studied in the region of photon energy 0.5–1.6 eV. Lines associated with the transitions hh,lh1-e1(1s,2s,3s), hh2,lh2-e2(1s,2s,3s), hh1,lh1-e2(1s) and hh3,lh3-e3(1s) had been revealed in reflection spectra. The shapes of the reflection and transparency lines had been calculated using a single oscillator model of dispersion relations and the Kramers–Kronig integrals. The binding energy of hh,lh1-e1 excitons, the effective mass m_hh^∗ and m_lh^∗ and the damping factor for the optical transitions to QW and QD had been determined. The lifetime of charge carriers on quantum dots varies in the range of 0.04–0.1 ps, while the radiative lifetime of excitons in quantum wells in the considered structure is around 2 ps.     

Redox Switches for Single‐Molecule Magnet Activity: An Ab Initio Insight

A dinuclear Co^II complex ( 1 ) featuring unprecedented anodic and cathodic switches for single‐molecule magnet (SMM) activity has been recently investigated (J. Am. Chem. Soc. 2013 , 135, 14670). The presence of sandwiched radicals in different oxidation states of this compound mediates magnetic coupling between the high‐spin (S=3/2) cobalt ions, which gives rise to SMM activity in both the oxidized ([ 1 (OEt₂)]⁺) and reduced ([ 1 ]^?) states. This feature represents the first example of a SMM exhibiting fully reversible, dual ON/OFF switchability. Here we apply ab initio and broken‐symmetry DFT calculations to elucidate the mechanisms responsible for magnetic properties and magnetization blocking in these compounds. It is found that due to the strong delocalization of the magnetic molecular orbital, there is a strong antiferromagnetic interaction between the radical and cobalt ions. The lack of high axiality of the cobalt centres explains why these compounds possess slow relaxation of magnetization only in an applied dc magnetic field.