Heteroleptic FeII Complexes of 2,2′‐Biimidazole and Its Alkylated Derivatives: Spin‐Crossover and Photomagnetic Behavior

Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO₄)₂?0.5H₂O ( 1 ), [Fe(TPMA)(XBIM)](ClO₄)₂ ( 2 ), and [Fe(TPMA)(XBBIM)](ClO₄)₂ ?0.75CH₃OH ( 3 ), were prepared by reactions of Fe^II perchlorate and the corresponding ligands (TPMA=tris(2‐pyridylmethyl)amine, BIM=2,2′‐biimidazole, XBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐biimidazole, XBBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐bibenzimidazole). The compounds were investigated by a combination of X‐ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T_1/2=190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T_1/2=196 K on cooling and 203 K on heating). Complex 3 is in the high‐spin state in the 2–300 K range. The difference in the magnetic behavior was traced to differences between the inter‐ and intramolecular interactions in 1 and 2 . The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3 , steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the Fe^II coordination environment, which stabilizes the high‐spin state of the complex. Both 1 and 2 exhibit a photoinduced low‐spin to high‐spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high‐spin state. For 1 , the decay rate constant follows the single‐exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high‐spin state at 50 K are similar to those determined for the high‐spin state at 295 K. This study shows that N‐alkylation of BIM has a negligible effect on the ligand field strength. Therefore, the combination of TPMA and BIM offers a promising ligand platform for the design of functionalized SCO complexes.     

Tangential extremal principles for finite and infinite systems of sets II: applications to semi-infinite and multiobjective optimization

This paper contains selected applications of the new tangential extremal principles and related results developed in Mordukhovich and Phan (Math Program 2011) to calculus rules for infinite intersections of sets and optimality conditions for problems of semi-infinite programming and multiobjective optimization with countable constraints.     

A parallel algorithm based on convexity for the computing of Delaunay tessellation

The paper describes a parallel algorithm for computing an n-dimensional Delaunay tessellation using a divide-conquer strategy. Its implementation (using MPI library for C) in the case n = 2, relied on restricted areas to discard non-Delaunay edges, is executed easily on PC clusters. We shows that the convexity is a crucial factor of efficiency of the parallel implementation over the corresponding sequential one.     

Synthesis of novel 6,11-O-bridged bicyclic ketolides via a palladium-catalyzed bis-allylation

A bridging chemistry process was developed to form an ether bridge between 6-O and 11-O of erythromycin A via a tandem or stepwise palladium-catalyzed bis-pi-allylation. By applying this bridging process, new 6,11-O-bridged bicyclic ketolides (BBKs) were synthesized. These BBKs showed good antibacterial activities against the macrolide-susceptible strains as well as mef-resistant strains and served as a good core for further modifications to study the structure-activity relationship (SAR) and to overcome bacterial resistance. [reaction: see text]     

Electrical and magnetic properties of CoFeAlO thin films

Influences of oxygen-partial pressure and annealing on the electrical and magnetic properties of CoFeAlO thin films were systematically investigated by means of resistivity, permeability, magnetization and ferromagnetic resonance (FMR) measurements. It was found that, with increasing oxygen-partial pressure or under annealing, the electrical resistivity of the film increased and the magnetic softness decreased, which is attributed to the microstructural change of the film. Interestingly, an as-deposited Co_45.30Fe_20.65Al_19.34O_14.71 film was found to exhibit an inverted hysteresis loop with negative coercivity, and this peculiar phenomenon disappeared upon effects of oxygen-partial pressure and annealing. It was also found that the as-deposited films owned a narrow FMR line width that increased with increasing oxygen-partial pressure or under annealing.     

High-frequency characteristics of CoFeVAlONb thin films

High-frequency characteristics of CoFeVAlONb thin films were studied. A thin film of Co_43.47Fe_35.30V_1.54Al_5.55O_9.93Nb_4.21 is observed to exhibit excellent magnetic properties; magnetic coercivity of 1.24 Oe, uniaxial in-plane anisotropy field of 66.99 Oe, and saturation magnetization of 19.8 kG. The effective permeability of the film is as high as 1089 and is stable up to 1.8 GHz, and with ferromagnetic resonance over 3 GHz. This film also has very high electrical resistivity of about 628 μΩ cm. These superior properties make it ideal for high-frequency magnetic applications.     

Derivation of Hartreeʼs theory for generic mean-field Bose systems

In this paper we provide a novel strategy to prove the validity of Hartree?s theory for the ground state energy of bosonic quantum systems in the mean-field regime. For the known case of trapped Bose gases, this can be shown using the strong quantum de Finetti theorem, which gives the structure of infinite hierarchies of k-particles density matrices. Here we deal with the case where some particles are allowed to escape to infinity, leading to a lack of compactness. Our approach is based on two ingredients: (1) a weak version of the quantum de Finetti theorem, and (2) geometric techniques for many-body systems. Our strategy does not rely on any special property of the interaction between the particles. In particular, our results cover those of Benguria–Lieb and Lieb–Yau for, respectively, bosonic atoms and boson stars.