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MgO-supported osmium dioxo species, described as Os(=O)2{−Osupport}1 or 2 (the brackets denote O atoms of the MgO surface), formed from Os3(CO)12 via supported Os(CO)2, and characterized by spectroscopy, microscopy, and theory, react with ethylene at 298 K to form osmium glycol species or with CO to give osmium mono- and di-carbonyls. Os(=O)2{−Osupport}1 or 2 is the precursor of a CO oxidation catalyst characterized by a turnover frequency of 4.0×10−3 (molecules of CO)/(Os atom×s) at 473 K; the active species are inferred to be osmium monocarbonyls. The structures and frequencies calculated at the level of density functional theory with the B3LYP functional bolster the experimental results and facilitate structural assignments. The lowest-energy structures have various osmium oxidation and spin states. The results demonstrate not only new chemistry of the supported single-site catalysts but also their complexity and the value of complementary techniques used in concert to unravel the chemistry. [ABSTRACT FROM AUTHOR]

New BN-embedded, thiophene-fused, polycyclic aromatic compounds with planar geometry were designed and synthesized. The molecules showed excellent stability and chemical robustness. Postfunctionalization on this skeleton was demonstrated with a series of electrophilic bromination, palladium-catalyzed cross-coupling, and Knoevenagel condensation reactions. The π skeleton remained intact during these late-stage transformations. The optical and electronic properties have been well tuned through incorporation of electron-rich and -deficient groups on the backbone. This work shows the great advantage of the postfunctionalization strategy on BN-containing polycyclic aromatic compounds for fast diversification and materials screening. [ABSTRACT FROM AUTHOR]

A new class of homologous gelators, LG12-(CH2) n-BSA, composed of bipyridinyl groups, L-glutamic moieties having double dodecyl chains, and linked alkyl spacers with different lengths were synthesized. It was found that these gelators could immobilize medium-polarity solvents readily and the behaviors of these gels showed a dependence on the spacer length. Of all the gels, the LG12-(CH2)11-BSA gels exhibited self-healing property and multiple-stimulus responsibility, such as heating, shaking, and sonication. The investigation of CD spectra indicated that the supramolecular chirality, which was attributed to the chiral transfer from the chiral center to the assemblies, was also closely related to the length of methylene spacers. The longer the alkyl spacers, the weaker the transmitted supramolecular chirality. Only LG12-(CH2)1-BSA gelators, which had the shortest spacers, formed right-handed nanoscale chiral twists owing to crowded hydrogen bonding interactions. Moreover, the high-polarity solvent DMF was found to be able to regulate the chiral twist as well as its pitch length readily. [ABSTRACT FROM AUTHOR]

The adsorption of N2 on structurally well-defined dealuminated HY zeolite-supported iridium diethylene complexes was investigated. Iridium dinitrogen complexes formed when the sample was exposed to N2 in H2 at 298 K, as shown by infrared spectra recorded with isotopically labeled N2. Four supported species formed in various flowing gases: Ir(N2), Ir(N2)(N2), Ir(C2H5)(N2), and Ir(H)(N2). Their interconversions are summarized in a reaction network, showing, for example, that, in the presence of N2, Ir(N2) was the predominant dinitrogen species at temperatures of 273-373 K. Ir(CO)(N2) formed transiently in flowing CO, and in the presence of H2, rather stable iridium hydride complexes formed. Four structural models of each iridium complex bonded at the acidic sites of the zeolite were employed in a computational investigation, showing that the calculated vibrational frequencies agree well with experiment when full calculations are done at the level of density functional theory, independent of the size of the model of the zeolite. [ABSTRACT FROM AUTHOR]

A new class of L-glutamic gelators, LG12(CH2) nCOOH, containing different lengths of methylene spacer were synthesized. It was found that the gelation ability of these compounds themselves was very weak. However, when another compound, p-xylylenediamine (XEA), was introduced, the gelation ability was improved greatly. In particular, LG12(CH2)10COOH showed super-gelation ability in the presence of XEA, which could immobilize almost all of the solvents except methanol. Moreover, the formed supramolecular gels even could be molded. Interestingly, some supramolecular gels of LG12(CH2) nCOOH and XEA could respond to multiple stimuli, such as heating, shaking, sonication, and acid/base. The studies of CD spectra suggested that the supramolecular chirality induced by self-assembled chiral gelator molecules in gels could be tuned by the length of methylene spacer. In addition, the supramolecular chirality could be regulated as on/off by heating-cooling or external NH3/HCl. This would facilitate the development of dual chiroptical switches by temperature and acid/base. [ABSTRACT FROM AUTHOR]

Supramolecular cages have been constructed by anion‐coordination‐driven assembly (ACDA) in recent years and have shown unique host‐guest interactions. However, most of the reported cages are made of the phosphate ion (PO43−); other anions have rarely been explored. Here we show for the first time that the sulfate ion (SO42−) is also able to form the A4L4 tetrahedral motif with tris‐bis(urea) ligands, but this is dependent on the stoichiometry of the sulfate ion (in solution). Notably, the sulfate cages display enhanced resistance for both Brønsted (pH as low as 4.3 in acetone containing 15 % water) and Lewis acids (metal complexes) compared to the corresponding phosphate cages, and thus could find applications where an acidic (proton or metals) environment is required. [ABSTRACT FROM AUTHOR]

Besides studies on the mineralization process, research on the demineralization of minerals provides another way to understand the crystallization mechanism of biominerals and fabricate crystals with complicated morphologies. The formation of ordered arrays of c-axis-oriented calcite microneedles with a tri-symmetric structure and lengths of more than 20 μm was realized on a large scale for the first time through anisotropic dissolution of calcite substrates in undersaturated aqueous solution in the presence of ammonium salts. The lengths and the aspect ratios of the calcite microneedles can be tuned by simply changing the concentrations of the ammonium salts and the dissolution time. The shape of the transverse cross sections of the calcite microneedles obtained in the presence of NH4Cl and NH4Ac is almost regularly triangular. The tri-symmetric transverse cross-section geometry of the calcite microneedles could be attributed to the tri-symmetric feature of rhombohedral calcite atomic structures, the synergetic interactions between electrostatic interaction of ammonium ions and dangling surface carbonate groups, and the ion incorporation of halide ions. [ABSTRACT FROM AUTHOR]

Monodisperse poly(acrylic acid)-modified Fe3O4 (PAA@Fe3O4) hybrid microspheres with dual responses (magnetic field and pH) were successfully fabricated. The PAA polymer was encapsulated into the inner cavity of Fe3O4 hollow spheres by a vacuum-casting route and photo-initiated polymerization. TEM images show that the samples consist of monodisperse porous spheres with a diameter around 200 nm. The Fe3O4 spheres, after modification with the PAA polymer, still possess enough space to hold guest molecules. We selected doxorubicin (DOX) as a model drug to investigate the drug loading and release behavior of as-prepared composites. The release of DOX molecules was strongly dependent on the pH value due to the unique property of PAA. The HeLa cell-uptake process of DOX-loaded PAA@Fe3O4 was observed by confocal laser scanning microscopy (CLSM). After being incubated with HeLa cells under magnet magnetically guided conditions, the cytotoxtic effects of DOX-loaded PAA@Fe3O4 increased. These results indicate that pH-responsive magnetic PAA@Fe3O4 spheres have the potential to be used as anticancer drug carriers. [ABSTRACT FROM AUTHOR]