Coordination-induced spontaneous resolution of a TPPE-based MOF and its use as a crystalline sponge in guest determination.

In this work, by virtue of a coordination-induced fixation of the propeller-like conformation of the tetraphenylethylene (TPE) backbone, we achieved a spontaneous resolution of conglomerate-forming enantiomers of [Co(TPPE)Cl2]·4DMF (1M and 1P), as unambiguously probed by single-crystal X-ray crystallography. Benefitting from the robust, accessible, and electron-rich 1D channels, the chiral MOF turned out to be a good 'crystalline sponge' to adsorb and determine six liquid guests, of which two (2-butanol and 2-butylamine) are crystallized in an enantiospecific manner.

Fluorescent LaVO4:Eu(3+) micro/nanocrystals: pH-tuned shape and phase evolution and investigation of the mechanism of detection of Fe(3+) ions.

LaVO4:Eu(3+) micro/nanocrystals with various shapes were hydrothermally synthesized by adjusting the pH of the system at 180 °C for 12 h in the presence of ethylenediaminetetraacetic acid (EDTA). The shape and phase of the final product were characterized by field emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD). Experiments showed that when the other conditions were kept unchanged, the shape of the final product changed from hollow microspheres constructed by nanorods to long nanorods, to short nanorods and finally to grains with microscale sizes with the pH increase from 4.0, 7.0, 11.0 to 13.0 in the system. Meanwhile, the t-LaVO4 phase was always obtained from the system at pH below 13.0 and the m-LaVO4 phase was formed at pH 13.0. It was found that the final product with various shapes presented different luminescence performances. LaVO4:Eu(3+) nanorods obtained from the system at pH 11.0 displayed the strongest luminescence and good fluorescence stability in water. Also, the above strong PL spectrum could be quenched by Fe(3+) ions without the interference of other ions, indicating that the present product could be used as an efficient fluorescent probe for highly selective detection of Fe(3+) ions in water systems. The fluorescence quenching mechanism was investigated simultaneously.

Synthesis and characterization of bisoxazolines- and pybox-copper(II) complexes and their application in the coupling of α-carbonyls with functionalized amines.

Binuclear complexes [{(DMOX)CuCl}2(µ-Cl)2] (1), mononuclear complexes [(DMOX)CuBr2] (2) (DMOX = 4,5-dihydro-2-(4,5-dihydro-4,4-dimethyloxazol-2-yl)-4,4-dimethyloxazole) and the pybox Cu(II) complex [(Dm-Pybox)CuBr2] (3) (Dm-Pybox = 2,6-bis[4',4'-dimethyloxazolin-2'-yl]pyridine) were obtained by reactions of CuX2 (X = Cl, Br) with DMOX and Dm-Pybox ligands, respectively. The molecular structures of 1, 2 and 3 have been determined by single-crystal X-ray diffraction analyses. The complexes 2 and 3 are efficient in catalyzing α-amination of ketones and esters through α-bromo carbonyl intermediate. The procedures are environmentally benign methods using molecular oxygen as an oxidant with water as the only byproduct.

Co9S8 nanotube arrays supported on nickel foam for high-performance supercapacitors.

Uniform Co9S8 nanotube arrays on conductive nickel foam were successfully synthesized through a facile two-step hydrothermal method and were directly applied as the electrode for high-performance electrochemical capacitors. The formation of the tubular structure of Co9S8 can be attributed to the nanoscale Kirkendall effect. SEM and TEM images show that most of the Co9S8 nanotubes have hexagonal sections. The diameter of the Co9S8 nanotubes is about 120-200 nm and the wall thickness is of 40-60 nm. Cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance measurements are applied to investigate the electrochemical performance of the Co9S8 nanotubes. The specific capacitance of the Co9S8 nanotubes is 1775 F g(-1) at 4 A g(-1), and 1483 F g(-1) at 24 A g(-1), indicating the high rate capability. Also, the Co9S8 nanotubes exhibit stable cycling performance.

Poly[aqua-(µ(5)-2-oxido-4-sulfonato-benzoato)lanthanum(III)].

The title compound, [La(C(7)H(3)O(6)S)(H(2)O)](n), forms a three-dimensional framework in which the asymmetric unit contains one La(III) atom, one 5-sulfosalicylate (2-oxido-4-sulfonatobenzoate) ligand and one coordinated water mol-ecule. The La(III) atom is coordinated by nine O atoms from three carboxyl-ate, three sulfonate and two hydroxyl groups, and one water mol-ecule, forming a distorted trigonal-prismatic square-face tricapped geometry.

Cannizzaro-type disproportionation of aromatic aldehydes to amides and alcohols by using either a stoichiometric amount or a catalytic amount of lanthanide compounds.

Aromatic aldehydes can be directly converted to the corresponding amides and alcohols in good to excellent yields by the treatment of aromatic aldehydes with lithium amide LiN(SiMe3)2 in the presence of catalytic lanthanide chlorides LnCl3 or by the treatment of aromatic aldehydes with a stoichiometric amount of lanthanide amides [(Me3Si)2N]3Ln(mu-Cl)Li(THF)3 at ambient temperature. The effects of solvents, substitutents on the phenyl ring, and lanthanide metals on the reaction have been examined. The mechanism of the disproportionation reaction was proposed based on the experimental results.

Homolysis of the Ln-N (Ln = Yb, Eu) bond. Synthesis, structural characterization and catalytic activity of ytterbium(II) and europium(II) complexes with methoxyethyl functionalized indenyl ligands.

The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied.