Urea coordinated titanium trichloride Ti(III)[OC(NH)2]6Cl3: a single molecular precursor yielding highly visible light responsive TiO2 nanocrystallites

A coordination complex, Ti(III)[OC(NH2)2]6Cl3, was first synthesized via reacting hot alcoholic solutions of TiCl3 and urea, which was subsequently employed as a molecular precursor for nanocrystalline TiO2 via thermal decomposition. Fourier transform IR spectroscopy confirmed C=O-->Ti coordination bond formation, while Rietveld refinement revealed a hexagonal crystal structure (space group: Pc1) for the complex with a = b = 16.438(4) A, c = 15.423(3) A, alpha = beta = 90 degrees , gamma = 120 degrees , and V = 3608.9(13) A3. Thermal decomposition and phase evolution processes of the complex were investigated in air by combined means of elemental analysis, Fourier transform IR, differential thermal analysis/thermogravimetry, X-ray diffraction, and Raman spectroscopy. Characterizations of the resultant TiO2 powders were achieved by scanning electron microscopy, high-resolution transmission electron microscopy, the Brunauer-Emmett-Teller analysis, thermal desorption spectroscopy, and UV-vis spectroscopy. Simultaneous doping of C, N, and Cl was realized upon pyrolyzing the molecular precursor in air, leading to significantly lowered direct and indirect interband transition energies of the resultant TiO2. As a consequence, the anatase nanopowders obtained at 450 and 500 degrees C, with specific surface areas of 97.8 and 64.1 m2/g, respectively, exhibit significantly higher efficiency than Degussa P25 in the bleaching of methyl orange solution under visible light (mainly consisting two wavelengths of 405 and 436 nm at 81:100 intensity ratio) irradiation, either at a fixed weight of TiO2 loading or at a fixed surface area of the loaded TiO2 powder.     

Infrared spectra and intensities of the H2O and N2 complexes in the range of the nu1- and nu3-bands of water

The IR spectra of complexes of water with nitrogen molecules in the range of the symmetric (nu(1)) and antisymmetric (nu(3)) bands of H(2)O have been studied in helium droplets. The infrared intensities of the nu(3) and nu(1) modes of H(2)O were found to be larger by factors of 1.3 and 2, respectively, in the N(2)-H(2)O complexes. These factors are smaller than those obtained in recent theoretical calculations. The conformation of the N(2)-H(2)O complex was estimated. Spectra and IR intensities of the (N(2))(2)-H(2)O and N(2)-(H(2)O)(2) complexes were also obtained and their structures are discussed.     

Aerobic Toluene Oxidation Catalyzed by Subnano Metal Particles

Subnanocatalysts (SNCs) containing various noble metals (Cu, Ru, Rh, Pd, or Pt) with sizes of approximately 1 nm were synthesized using dendritic poly(phenylazomethine)s as a macromolecular template. These materials exhibit high catalytic performance during toluene oxidation without the use of harmful solvents or explosive oxidants, resulting in the formation of valuable organic products, including benzoic acid as the major product. In particular, Pt₁₉ SNC with a narrow particle size distribution exhibits extraordinary catalytic activity, with a turnover frequency of 3238 atom^?1 h^?1, which is 1700 times greater than that obtained by commercial Pt/C catalysts.     

Conformational analysis of N-aryl-N-(2-azulenyl)acetamides

Aromatic amides bearing 2-azulenyl group on the amide nitrogen were synthesized and their structures were investigated. The π-electron density of the N-aryl group was found to influence the cis-trans conformational preferences of these compounds in solution. X-ray crystallography revealed that the plane of the 2-azulenyl ring has a strong tendency to lie coplanar with the amide plane when the azulene group is located on the same side as the amide oxygen atom.     

Chemical and optical control of peristaltic actuator based on self-oscillating porous gel

We demonstrate the chemical and optical control of the self-sustaining peristaltic motion of a structural colored porous hydrogel.     

Catalytic enantioselective allylation of aldehydes using β-amido functionalized allylstannanes with chiral In(OTf)3/i-Pr-pybox complexes

The enantioselective allylation of aldehydes using a variety of β-amido functionalized allyltributylstannanes proceeded smoothly with good to high yields and enantioselectivities in the presence of 10 mol % of a chiral catalytic complex prepared from In(OTf)₃ and 2,6-bis[(S)-4-isopropyloxazolin-2-yl]pyridine {(S)-i-Pr-pybox}, providing the corresponding chiral γ-hydroxy amides.     

Nuclear spin conversion of methane in solid parahydrogen

The nuclear spin conversion of CH(4) and CD(4) isolated in solid parahydrogen was investigated by high resolution Fourier transform infrared spectroscopy. From the analysis of the temporal changes of rovibrational absorption spectra, the nuclear spin conversion rates associated with the rotational relaxation from the J=1 state to the J=0 state for both species were determined at temperatures between 1 and 6 K. The conversion rate of CD(4) was found to be 2-100 times faster than that of CH(4) in this temperature range. The faster conversion in CD(4) is attributed to the quadrupole interaction of D atoms in CD(4), while the conversion in CH(4) takes place mainly through the nuclear spin-nuclear spin interaction. The conversion rates depend on crystal temperature strongly above 3.5 K for CH(4) and above 2 K for CD(4), while the rates were almost constant below these temperatures. The temperature dependence indicates that the one-phonon process is dominant at low temperatures, while two-phonon processes become important at higher temperatures as a cause of the nuclear spin conversion.