High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Well-posedness of two pseudo-parabolic problems for electrical conduction in heterogeneous media

We prove a well-posedness result for two pseudo-parabolic problems, which can be seen as two models for the same electrical conduction phenomenon in heterogeneous media, neglecting the magnetic field. One of the problems is the concentration limit of the other one, when the thickness of the dielectric inclusions goes to zero. The concentrated problem involves a transmission condition through interfaces, which is mediated by a suitable Laplace-Beltrami type equation.     

Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Mössbauer studies of EFG of the different57Fe(57Co)-Oxygen configurations in oriented Y−Ba−Cu−O

We have determined the various parameters of the electric field gradient (EFG) for different Fe-oxygen configurations. This was achieved by analyses of a variety of spectra using a procedure which allows fitting of all spectra of oriented 1-2-3 compounds obtained at different tilt angles β simultaneously, taking into account the degree of texture. The use of a point charge model is invalidated because of the high degree of estimated covalence. The Mössbauer parameters are rationalized. The absence of any observed anisotropy of the mean square displacement of the dopant at the Cu(1) site is rather intriguing.     

Photopolymerization of methyl methacrylate with the use of bromine as photoinitiator

Low concentrations of bromine (0.008–0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04–0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems.     

Is cluster evaporation statistical? A comparison of simulation results for Ar13 with exact classical phase space theory

We have simulated the dissociation reactionA _n →A _n?1+A for small clusters (L-J argon) with well defined internal energy and total angular momentum. Reaction rates and kinetic energy release distributions are compared to the predictions of several statistical theories, including RRK, the “Engelking” model, and phase space theory (PST). We have applied classical phase space theory in an essentially exact formulation using accurate anharmonic vibrational densities of states (and no adjustable parameters). We present a critical evaluation of the different theories and sensitivity of the results to the underlying assumptions.     

Linear and nonlinear substructured Restricted Additive Schwarz iterations and preconditioning

Iterative substructuring Domain Decomposition (DD) methods have been extensively studied, and they are usually associated with nonoverlapping decompositions. It is less known that classical overlapping DD methods can also be formulated in substructured form, i.e., as iterative methods acting on variables defined exclusively on the interfaces of the overlapping domain decomposition. We call such formulations substructured domain decomposition methods. We introduce here a substructured version of Restricted Additive Schwarz (RAS) which we call SRAS. We show that RAS and SRAS are equivalent when used as iterative solvers, as they produce the same iterates, while they are substantially different when used as preconditioners for GMRES. We link the volume and substructured Krylov spaces and show that the iterates are different by deriving the least squares problems solved at each GMRES iteration. When used as iterative solvers, SRAS presents computational advantages over RAS, as it avoids computations with matrices and vectors at the volume level. When used as preconditioners, SRAS has the further advantage of allowing GMRES to store smaller vectors and perform orthogonalization in a lower dimensional space. We then consider nonlinear problems, and we introduce SRASPEN (Substructured Restricted Additive Schwarz Preconditioned Exact Newton), where SRAS is used as a preconditioner for Newton’s method. In contrast to the linear case, we prove that Newton’s method applied to the preconditioned volume and substructured formulation produces the same iterates in the nonlinear case. Next, we introduce two-level versions of nonlinear SRAS and SRASPEN. Finally, we validate our theoretical results with numerical experiments.