Topological and Steric Constraints to Stabilize Heteroleptic Copper(I) Complexes Combining Phenanthroline Ligands and Phosphines

Heteroleptic copper(I) complexes combining phenanthroline derivatives (NN) and chelating bisphosphine ligands (PP) are an important class of luminescent materials for various applications. Although thermodynamically stable, [Cu(NN)(PP)]⁺ derivatives are also kinetically unstable. As a result, a dynamic ligand-exchange reaction is often observed in solution, leading to a dynamic mixture of heteroleptic and homoleptic complexes. To prevent the formation of the homoleptic species, macrocyclic phenanthroline ligands have been used for the preparation of [Cu(NN)(PP)]⁺ pseudorotaxanes. The topological constraint resulting from the macrocyclic structure of the NN ligand drives the thermodynamic equilibrium towards the exclusive formation of the heteroleptic complex as long as the macrocycle is large and flexible enough to allow for the threading of the PP ligand. Conversely, when the threading is prevented by steric constraints, unprecedented copper(I) complexes with a trigonal coordination geometry are obtained. These results are summarized in the present concept article.     

Optoelectronic,Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λ_max=427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended π-conjugated groups cause a redshift, whereas electron-withdrawing groups result in a blueshift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λ_PL=525–578 nm) with quantum yields of up to 18 % and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (E_ox1=0.62–1.02 V vs. Fc/Fc⁺) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state.     

Influence of heat treatment temperature of carbon fiber felt substrate on polyaniline electrosynthesis and its properties

Journal of Solid State Electrochemistry - Polyaniline was electrosynthesized using three voltammetric cycles on carbon fiber felts annealed at 1400, 1600, 2000, and 2300 K. Felts and...     

Drag Force Calculations in Polydisperse DEM Simulations with the Coarse-Grid Method: Influence of the Weighting Method and Improved Predictions Through Artificial Neural Networks

Transport in Porous Media - Several methods are employed for drag force calculations with the discrete element method depending on the desired accuracy and the number of particles involved. For...     

Equivalence of Ensembles,Condensation and Glassy Dynamics in the Bose–Hubbard Hamiltonian

Journal of Statistical Physics - We study mathematically the equilibrium properties of the Bose–Hubbard Hamiltonian in the limit of a vanishing hopping amplitude. This system conserves the...     

Convergence rate of inertial Forward–Backward algorithm beyond Nesterov’s rule

Mathematical Programming - In this paper we study the convergence of an Inertial Forward–Backward algorithm, with a particular choice of an over-relaxation term. In particular we show that...     

Interaction between asymmetrical damping and geometrical nonlinearity in vehicle suspension systems improves comfort

Nonlinear Dynamics - This work explores the role of asymmetrical damping and geometrical nonlinearities in the suspension system of a simplified vehicle model in order to improve comfort. Improving...     

Invariant measures for the horocycle flow on periodic hyperbolic surfaces

We classify the ergodic invariant Radon measures for the horocycle flow on geometrically infinite regular covers of compact hyperbolic surfaces. The method is to establish a bijection between these measures and the positive minimal eigenfunctions of the Laplacian of the surface. Two consequences arise: if the group of deck transformations G is of polynomial growth, then these measures are classified by the homomorphisms from G ₀ to ℝ where G ₀ ≤ G is a nilpotent subgroup of finite index; if the group is of exponential growth, then there may be more than one Radon measure which is invariant under the geodesic flow and the horocycle flow. We also treat regular covers of finite volume surfaces. The first author was supported by NSF grant 0500630. The second author was supported by NSF grant 0400687.     

On a Modified Subgradient Algorithm for Dual Problems via Sharp Augmented Lagrangian*

We study convergence properties of a modified subgradient algorithm, applied to the dual problem defined by the sharp augmented Lagrangian. The primal problem we consider is nonconvex and nondifferentiable, with equality constraints. We obtain primal and dual convergence results, as well as a condition for existence of a dual solution. Using a practical selection of the step-size parameters, we demonstrate the algorithm and its advantages on test problems, including an integer programming and an optimal control problem. *Partially Supported by 2003 UniSA ITEE Small Research Grant Ero2. Supported by CAPES, Brazil, Grant No. 0664-02/2, during her visit to the School of Mathematics and Statistics, UniSA.