The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

Differential pulse anodic stripping voltammetric determination of traces of copper with a tobramycin-Nafion modified electrode.

A Nafion-modified glassy carbon electrode incorporated with tobramycin for the voltammetric stripping determination of Cu2+ has been explored. The electrode was fabricated by tobramycin containing Nafion on the glassy carbon electrode surface. The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu2+ compared with a bare glassy carbon electrode and the Nafion modified electrode. Cu2+ was accumulated in HAc-NaAc buffer (pH 4.6) at a potential of -0.6 V (vs. SCE) for 300 s and then determined by differential pulse anodic stripping voltammetry. The effects of various parameters, such as the mass of Nafion, the concentration of tobramycin, the pH of the medium, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 1.0 x 10(-9) to 5.0 x 10(-7) mol l(-1) with a correlation coefficient of 0.9971. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 x 10(-8) and 2.0 x 10(-7) mol l(-1) Cu2+, respectively. The detection limit (three times signal to noise) was 5.0 x 10(-10) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determination of copper in water samples, and also in analytical reagent-grade salts with satisfactory results.     

Determination of polymeric aluminum in soil extracted with a modified anion-exchange resin as a solid-phase adsorbent by ICP-AES.

In the present work, a new method was established by applying solid-phase extraction (SPE) to preconcentrate and separate polymeric aluminum (Al) and using ICP-AES to determine the polymeric Al, the total monomeric Al, and the total Al in soil extracts, respectively. A modified resin was prepared with impregnated 8-hydroxyquinoline-5-sulfoxinate (HQS) on the anion-exchange resin. It has good recognition ability for Al fractions, compared to the commonly used cation ion-exchange resin, which has a better ability to adsorb cations and a weak ability to recognize detailed Al species. The optimum conditions for Al fractionation sorption, elution and separation and the interference of foreign ions were studied with the prepared resin by continuous column and batch procedures. Monomeric Al was bound to Pyrocathecol Violet (PCV) at pH 6.2, whereas the polymeric Al species did not react with PCV for at least 15 min. Because a stable complex of Al-PCV was not absorbed on the HQS modified resin, the polymeric Al could be preconcentrated on-line by the HQS-modified resin. The adsorbed polymeric Al was eluted with 3 mL of 3 mol L(-1) of HCl, and then detected by ICP-AES. The method has been applied to directly determine polymeric Al in soil extracts with high selectivity as well as a high preconcentration factor. It gives a limit of detection of 0.6 ng mL(-1) with a relative standard deviation of less than 5.7% (n = 5, 0.24 microg mL(-1) Al).     

Structural effects of multiple-bonds on aggregating tendencies of long-chain esters

The kinetics of the hydrolysis of p-nitrophenyl esters of three types of single-chain carboxylic acids, namely, saturated, olefinic and acetylenic, was investigated in two aquiorgano binary solvent systems, DMSO-H₂O and dioxane (DX)-H₂O. The ester probes used are: octanoic (C8), dodecanoic (C12) , stearic (C18) , oleic (C18-ol) , elaidic (C18-el ) and stearolic (C18-st). The order of measured CAgC values is: C18-ol>C18-el>C18>C18-st, whereas the order of decreasing magnitude of the observed hydrolytic rate constants of the monomeric species (k_m) is: C18>C18-el>C18-ol> C18-st. These rather unanticipated results are discussed.     

Studies on the method of total synthesis of koumine: I. 4-Substituted 1,2-dihydropyridine derivatives and their function as a conjugated diene in Diels-Alder reaction

A route to the total synthesis of koumine has been suggested. Five 4-substituted 1, 2-d hydropyridine derivatives, which are supposed to be a conjugated diene of Diels-Alder reaction to produce the isoquinuclidine ring of koumine, have been synthesized. Only two of them were found to be able to undergo the Diels-Alder reaction. The stereochemistry of the reaction product has also been examined.     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004