Three Bis‐BODIPY Analogous Diruthenium Redox Series: Characterization and Electronic Structure Analysis

The dianion derived from (2Z,6Z)‐3,7‐diphenyl‐N2,N6‐di(pyridin‐2‐yl)pyrrolo[2,3‐f]indole‐2,6(1H,5H)‐diimine (H₂BL), a modified BODIPY ligand precursor, is shown to be capable of bridging two metal complex fragments RuL₂, L=2,4‐pentanedionato (acac^?), 2,2’‐bipyridine (bpy) or 2‐phenylazopyridine (pap) in [Ru(acac)₂Ru(μ‐BL)Ru(acac)₂] ( 1 / 2 ), [Ru(bpy)₂Ru(μ‐BL)Ru(bpy)₂](ClO₄)₂ ([ 3 ](ClO₄)₂) and [Ru(pap)₂Ru(μ‐BL)Ru(pap)₂](ClO₄)₂ ([ 4 ](ClO₄)₂). The compounds, including a diastereoisomeric pair 1 (meso) and 2 (rac) were spectroscopically and structurally characterized. Reversible electron transfers as revealed by cyclic and differential pulse voltammetry allowed for an EPR and UV‐vis‐NIR spectroelectrochemical investigation of several neighboring charge states. Together with susceptibility measurements and TD‐DFT calculations the assignment of oxidation states reveals that 1 , 2 are diruthenium(III) species which can be oxidized or reduced by one electron whereas 3 ²⁺ and 4 ²⁺ contain ruthenium(II) and get reduced or oxidized mainly at the dianionic bridge ( 3 ²⁺) or are reduced at the ancillary ligands pap ( 4 ²⁺).     

Proton transfer rate‐equilibria in apolar aprotic solvents: a historical perspective

Low dielectric constant apolar aprotic solvents, although employed on a limited scale for studying proton transfer reactions as compared with commonly used polar protic or dipolar aprotic ones, offer some particular advantages, namely, specific solute–solvent interactions are virtually eliminated and proton transfer occurs directly in an apolar aprotic solvent. An intriguing feature of these reactions is their general acid‐catalyzed/base‐catalyzed kinetics with a time scale over microseconds to minutes. In fact, the true or intrinsic relative strengths of acids/bases when measured in such solvents come to the fore much more clearly than those obtained in other classes of solvents. Recently, a review documenting the post‐1980 developments relating to proton transfer reactions in apolar aprotic solvents has been published. The present article is a commentary of the pre‐1980 developments in this area since the 1920s Brønsted–Lowry's “proton cult” of acid–base theory. Copyright © 2016 John Wiley & Sons, Ltd.     

η-π0 mixing and ψ′ → ψπ0 decay

The ψ′ → ψπ⁰ decay rate is studied in a chiral symmetry breaking scheme by including effects from π⁰-η mixing only. The result obtained is in very good agreement with the experiment.     

Strong phase separation in a model of sedimenting lattices

We study the steady state resulting from instabilities in crystals driven through a dissipative medium, for instance, a colloidal crystal which is steadily sedimenting through a viscous fluid. The problem involves two coupled fields, the density and the tilt; the latter describes the orientation of the mass tensor with respect to the driving field. We map the problem to a one-dimensional lattice model with two coupled species of spins evolving through conserved dynamics. In the steady state of this model each of the two species shows macroscopic phase separation. This phase separation is robust and survives at all temperatures or noise levels- hence the term strong phase separation. This sort of phase separation can be understood in terms of barriers to remixing which grow with system size and result in a logarithmically slow approach to the steady state. In a particular symmetric limit, it is shown that the condition of detailed balance holds with a Hamiltonian which has infinite-ranged interactions, even though the initial model has only local dynamics. The long-ranged character of the interactions is responsible for phase separation, and for the fact that it persists at all temperatures. Possible experimental tests of the phenomenon are discussed.     

Kinetics of proton transfer between metasubstituted benzoic acids and the carbinol base of crystal violet in toluene: Specific solvent effect–free metasubstituent effect on the reactivity of benzoic acids

Apolar aprotic solvents are particularly advantageous for investigating the intrinsic metasubstituent effect free from complications of specific solvent effects. A kinetic study for toluene‐phase proton transfers between meta‐Me, F, Cl, Br, I, OMe, OPh, COPh, CF₃, CN, NO₂, H benzoic acids and Crystal Violet carbinol base has shown the forward rate constant (log k₁) the most appropriate reactivity parameter in toluene. log k₁ (toluene) as compared to other reported reactivity parameters in benzene or toluene have been found more sensitive to the metasubstituent effect. The regression results of the correlation of log k₁ (toluene) of the acids according to the four dual substituent parameter models are statistically significant, and the best result has been obtained using Taft's model. The overall analysis reveals that metasubstituent's effect is exerted by a 65:35 pattern of its field and second‐order resonance effects. The results further demonstrate that a metasubstituent's resonance effect is virtually a relayed universal field/inductive effect. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 303–311, 2011     

On results of G. Brosch and T.C. Alzahary

We prove a uniqueness theorem for two non-constant meromorphic functions sharing three values which improves a recent result of T.C. Alzahary. As a consequence of our main result we also improve a theorem of G. Brosch.     

Effect of polarization on two-dimensional carrier distribution in nitride quantum wells

Wide band-gap group-III nitrides are important for the design of optical devices in the blue and blue–green region. Owing to their wurtzite structure, these materials have a strong inherent polarization field that affects carrier distribution, exciton stability and hence influences the optical properties of the devices. So far, carriers have been assumed to have a sheet-like character. In this paper a non sheet-like distribution function for these quasi two-dimensional carriers is proposed that incorporates the effect of the polarization field. Here GaN/InGaN/GaN and AlGaN/GaN/AlGaN quantum wells have been studied. The polarization field causes the electron and hole wave functions to separate out, thus causing decrease of emission strength and strong reduction of exciton binding energy. This treatment explains well the qualitative nature of carrier distribution in the well. The polarization field changes with GaN mole fraction present in the tertiary nitride layer. The effect of mole fraction on carrier distribution has also been studied. It is found that, inside the well, the hole distribution changes a little more with change in mole fraction than the electron distribution, but for all practical purposes the net change in the distribution pattern is negligible.     

Analysis of Ti:LiNbO3 zero-gap directional coupler for wavelength division multiplexer/demultiplexer

For the purpose of multichannel integrated-optical wavelength division MUX/DEMUX design, the wavelength tuning method of Ti:LiNbO₃ zero-gap directional coupler is analysed by effective-index based matrix method (EIMM). In this method, first, the 2D refractive index profile of the Ti:LiNbO₃ zero-gap directional coupler is transformed into lateral 1D effective-index profile by WKB method. Finally, matrix method is applied to this effective-index profile and the propagation constants are computed from the resonance peaks of the excitation efficiency versus propagation constant characteristics. It has been shown that the channel wavelength tuning can be achieved by varying the Y-branching angle at the input and output of the device or by a slight variation of two-mode-section length. The method of electro-optic fine tuning of the channel wavelength and channel separation of the device has also been investigated. A cascaded structure with proper parameters for four-channel application is also simulated and the results are presented.