Robust core-shell supramolecular assemblies based on cationic vesicles and ring-shaped [Mo154] polyoxomolybdate nanoclusters: template-directed synthesis and characterizations

Substantial progress has been made recently in extending the supramolecular assembly of biomimetic structures to vesicle-based sophisticated nanocomposites and mesostructures. We report herein the successful preparation of unilamellar surfactant vesicles coated with a monolayer of ring-shaped [Mo(154)] polyoxometalate (POM) nanoclusters, (NH(4))(28)[Mo(154)(NO)(14)O(448)H(14)(H(2)O)(70)]. approximately 350 H(2)O, by coulomb attractions using preformed didodecyldimethylammonium bromide (DDAB) surfactant vesicles as templates. The resultant vesicle-templated supramolecular assemblies are robust (they do not disintegrate upon dehydration) both at room-temperature ambient and vacuum conditions, as characterized by conventional transmission electron microscopy (TEM) and atomic force microscopy (AFM). The flexibility of the complex soft assemblies was also revealed by AFM measurements. The effect of POM-vesicle coulomb attractions on the dimensions of the templating vesicles was also investigated by using dynamic light scattering (DLS). Although origins of the structure stability of the as-prepared supramolecular assemblies are not clear yet, the nanometer scale cavities and the related properties of macroions of the POM clusters may play an important role in it.     

集化学家与化学教育家于一身的一代化学大师李比希--纪念李比希诞辰200周年

在德国著名化学家李比希诞辰200周年之际，对这位集化学家与化学教育家于一身的一代化学大师对科学和科学教育以及人类社会作出的贡献进行了评述。     

Synthesis and magnetic properties of novel polymeric complexes containing bithiazole rings

A novel linear polymer (PFABT) containing bithiazole rings was synthesized by polycondensation of 2,2′‐diamino‐4,4′‐bithiazole (DABT) and formaldehyde. The complexes of PFABT with two transition metal ions (Fe²⁺, Cu²⁺) were prepared for the first time. The polymer was determined through FT‐IR, ¹H‐NMR and elemental analysis (EA), and the complexes were characterized by FT‐IR. The magnetic behaviors of these complexes were measured as a function of magnetic field strength (0–50 kOe) at 4 K and as a function of temperature (4–300 K) under an applied magnetic field of 30 kOe. The results show that PFABT‐Cu²⁺ is a ferromagnet while PFABT‐Fe²⁺ is an anti‐ferromagnet. Copyright © 2007 John Wiley & Sons, Ltd.     

Click Chemistry: Evolving on the Fringe

The article herein briefly introduces the story of the birth of click chemistry and its evolution after that. A new angle to interpret click reactions was proposed using the “reactivity‐availability‐functionality” trilogy. CuAAC (Copper‐catalyzed azide‐alkyne cycloaddition), the most popular click reaction by far, was revisited along with the thiol‐ene, metal‐free AAC, SuFEx (Sulfur(VI) fluoride exchange) and the lately discovered diazotransfer process. By encountering more and more near‐perfect reactions, click chemistry is evolving and expanding on the fringe of the chemistry and different scientific disciplines, destination unknown.      

含吩噻嗪金属配合物的合成及非线性光学性质研究

本文报道了一种新的配体:10-乙基-3-甲酰吩噻嗪缩肼基二硫代甲酸甲酯(HL)及其金属配合物的合成。采用了元素分析、质谱、核磁共振、红外光谱对配体及其金属配合物进行了表征。此外,并应用紫外、荧光和Z-扫描技术,测定了配体及其金属配合物的荧光最佳发射波长(λ_max^em)、荧光量子产率(Φ_f)、寿命(τ)和非线性光学性质。结果表明它们在DMF溶液中都能发射出较强的橄榄色荧光,配体及其金属配合物都有双光子吸收,并且金属配合物的非线性光学效应比配体明显增强。用半经验量子化学方法(RHF/PM3)计算结果与实验值较为吻合。     

Molecular beams and model catalysis: activity and selectivity of specific reaction centers on supported nanoparticles.

Reaction kinetics on nanometer-scale particles are different from those on extended surfaces of bulk materials. This fact has been utilized for a long time to empirically maximize the performance of heterogeneous catalysts, but the understanding of the underlying effects is poor at the microscopic level. Modern molecular beam-based methods, however, allow us to derive very detailed kinetic information on catalytically active surfaces. In combination with structurally highly controlled model catalysts, microscopic insights into the activity and selectivity of specific reaction centers on catalyst nanoparticles can be obtained. This combined approach is illustrated through simple model reactions.     

A theoretical evaluation of steric and electronic effects on the structure of [OSO4 (NR3)] (NR3 = bulky chiral alkaloid derivative) complexes

Summary The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO₄(NR₃)] (NR₃ = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR₃, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference.