Sumanenemonoone Imines Bridged by Redox‐Active π‐Conjugated Unit: Synthesis,Stepwise Coordination to Palladium(II), and Laser‐Induced Formation of Nitrogen‐Doped Graphitic Carbon

Sumanenemonoone imine compounds bridged by a redox‐active π‐conjugated unit on the basis of the conversion between 1,4‐phenylenediamine and 1,4‐benzoquinonediimine were synthesized and characterized. The stepwise coordination of the imino groups to Pd^II in the sumanenemonoone imine compound bridged by 1,4‐benzoquinonediimine was indicated by the titration experiment. Laser irradiation of a film of the metal‐free quionediimine gave nitrogen‐doped graphitic carbon, which was supported by an increase in conductivity and by Raman spectroscopy. The obtained graphitic carbon corresponds to carbonous compounds thermally treated at approximately 700–1000 °C. The ratio of nitrogen and carbon relative to that in the starting compound was nearly completely retained (5.4 % decrease).     

Size‐Selective Complexation and Extraction of Endohedral Metallofullerenes with Cycloparaphenylene

A new strategy for the non‐chromatographic extraction of metallofullerenes from solutions of arc‐processed raw soot is based on the size‐selective complexation with cycloparaphenylene (CPP). [11]CPP has a high affinity for M_x@C₈₂ (x=1, 2); for example, Gd@C₈₂ can be selectively extracted from a fullerene mixture by the addition of [11]CPP. This approach should open new opportunities in metallofullerene chemistry, including for the bulk extraction of metallofullerenes.     

Thiophene‐Based,Radial π‐Conjugation: Synthesis,Structure, and Photophysical Properties of Cyclo‐1,4‐phenylene‐2′,5′‐thienylenes

The synthesis of cyclo‐1,4‐phenylene‐2′,5′‐thienylenes (CPTs) as the first example of a thiophene‐based, radially π‐conjugated system is described. X‐ray crystal structures, UV‐vis absorption and emission spectra, and theoretical studies revealed the unique structural and photophysical properties of CPTs. With all of these unique structural and photophysical properties, the radially π‐conjugated CPTs are expected to open a door for the discovery and development of new functional organic materials.     

Influence of various additives on the sorption of cesium from strong nitric acid medium on potassium cupric ferrocyanide

The inhibitory action of hydrazinium or amidosulfate ion, whose presence prevented the oxidation of potassium cupric ferrocyanide with nitric acid and thereby kept the distribution coefficient of Cs on the sorbent at very high values in strong nitric acid medium, was eluciated to be due to the removal of nitrous acid present as an impurity. Based on this interpretation, a number of chemicals capable of reacting with nitrous acid were found to be effective as inhibitors besides hydrazinium and amidosulfate ions. A new process for Cs separation was proposed on the basis of the result obtained.     

Design and Synthesis of Carbon Nanotube Segments

The selective and predictable synthesis of structurally uniform carbon nanotubes (CNTs) represents a long‐standing goal in both nanocarbon science and synthetic organic chemistry. This Review focuses on synthetic studies toward the controlled synthesis of CNTs with single chirality through the organic synthesis of CNT segments and the organic template assisted growth of CNTs.     

Chemoselective conjugate addition of dimethylzinc-mediated ether and acetal radicals to alkylidenemalonates and asymmetric reactions

Cyclic and acyclic ether or acetal radicals were generated directly from ethers or acetals by the action of dimethylzinc-air, and their subsequent conjugate addition reaction with alkylidenemalonates afforded the corresponding conjugate adducts in reasonably high yields. The reaction with benzylidenemalonates bearing formyl and imino groups gave chemoselectively the conjugate addition products. The asymmetric reaction of bis(8-phenylmenthyl) benzylidenemalonate proceeded diastereoselectively to provide the adduct with 93:7 dr.     

Synthesis and photoproperties of Eu(III)‐bearing star polymers as luminescent materials

Water‐soluble luminescent material was developed by introducing europium (Eu(III)) ions into the core of a star polymer. Living radical polymerization was used to obtain the star polymer. The strategy to introduce Eu(III) ions into the star polymer was studied using poly(methyl methacrylate) as an arm. The best Eu(III) ion introduction was obtained by simultaneous introduction, resulting in about 30 µmol/g‐polymer, which needed only one step for synthesis. The utilization of a hydrophilic polymer such as poly(ethylene oxide) (PEO) as an arm produced a water‐soluble star polymer. The Eu(III)‐bearing PEO star polymer obtained in this study was water soluble and showed fluorescence. In addition, it was stable in water after 1 month. The Eu(III)‐bearing star polymer exhibited luminescent properties under UV light irradiation with relatively high quantum yields of 60% in organic solution and 19% in aqueous solution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2527–2535     

Aziridinofullerene: a versatile platform for functionalized fullerenes

An aziridine moiety on the fullerene core can serve as an acid-triggered reacting template for the controlled synthesis of a range of functionalized fullerenes that are otherwise difficult to synthesize in an efficient and selective manner. A copper-catalyzed aziridination of C(60) for the practical synthesis of aziridinofullerene 1 and acid-catalyzed reactions of 1 with mono- and bifunctional nucleophiles as well as alkynes are described. The rapid generation of structural diversity in a single chemical operation using the common platform 1 is notable.