Behavior of vanadium dioxide single crystals synthesized under the various oxygen partial pressures at 1500 K

The effects of nonstoichiometry upon the behavior of vanadium dioxide single crystals in the vicinity of the semiconductor/metal transition temperature (T_c) were experimentally investigated. According to the electrical and thermal measurements, more stoichiometric vanadium dioxide exhibited the less electrical conductivity gap, the larger thermal and electrical hysteresis, and the lower transition temperature than the increased nonstoichiometric one near transition. Infrared absorptions and X-ray observations indicated the local and overall lattice distortion in the nonstoichiometric crystal due to the existence of V⁵⁺ ions. Furthermore, an intermediate phase between the low-temperature monoclinic and the high-temperature tetragonal phases was found in the nonstoichiometric VO₂. On the other hand, no evidence for this intermediate phase was found in the stoichiometric one. Finally, some comparisons and discussions of our present data with the previously published ones were made.     

Synthesis of new 18-substituted analogues of calcitriol using a photochemical remote functionalization

A novel convergent synthetic approach to new analogues of calcitriol modified at the C-18 position is reported. The key step in the synthesis is the 20-hydroxyl-directed photochemical iodination of the 18-methyl group in the presence of (diacetoxyiodo)benzene. Using this methodology, two new analogues of calcitriol were prepared: the first contains a hydroxylated alkyl side chain attached at C-18 with the natural side chain replaced by an isopropylidene group; the second is a conformationally locked analogue due to an extra oxacycle between the C-18 and C-20 positions.     

Simulated T ← S spectra of benzaldehydes as a function of the energy gap between the ππ and nπ levels

The T_1,2 ← S₀ spectra of benzaldehydes have been studied as a function of the energy separation between the vibrationless levels. It is shown that the spectra are very complicated in the region of ΔE[T₂⁰(nπ^*)-T₁⁰(ππ^*)] = 250–400 cm⁻¹, reflecting effective vibronic interferences between T₂⁰(0-0) and each of the ν₃₆-ν₃₃ out-of-plane vibrational levels of T₁⁰(ππ^*). The simulated spectra correspond to the observed spectra. In the case of T₁⁰ = ³nπ^* and T₂⁰ = ³ππ^* the spectral change is not so drastic as in the reverse case loc. cit. because the optical intensity generally concentrates in the longest wavelength band, i.e., the origin band of the T₁(nπ^*) ← S₀ transition. The simulation spectra are useful for interpretation of the absorption spectra in similar electronic structure systems of substituted benzaldehydes.     

Absorption and emission spectra of the lowest triplet state in hexachloroacetone

T₁ ← S₀ absorption and T₁ → S₀ phosphorescence spectra of neat cystalline hexachloroacetone have been analyzed at 4.2°K. From the lifetime and energy the upper state is assigned as ³nπ^*. The spectra are sharp compared to other aliphatic ketones, with the 0-0 band at 26 248 ± 2 cm ^?1. The phosphorescence shows two strong progressions; one involving the CO stretching mode at 1784 cm^?1 (x), the other a long progression of at least 8 bands involving a mode at 143 cm^t-1 (a). The 143 cm^?1 progression forming mode can best be asigned to the CO out-of-plane wagging vibration. The absorption shows the same two strong progressions, reduced in frequency to 1270 cm^t-1 and 123 cm^?1, respectively, but with the progression in mode a broadened with increasing n. The broadening is interpreted as arising from inversion doublets; the close harmonicity up to n = 5 allowing the potential barrier to inversion to be estimated as > 700 cm^?1. A feature of the spectra is the absence of low frequency torsional modes suggesting lack of pseudo Jahn-Teller distortion of the triplet state potential surface. For comparison, the phosphorescence of crystalline hexafluoroacetone was also studied at 4.2°K. The spectrum exhibits broad bandedness with a 00 band tentatively assigned at 26 870 ± 20 cm^?1.     

Incorporation of titanium dioxide particles into polymer matrix using block copolymer micelles for fabrication of high refractive and transparent organic–inorganic hybrid materials

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles into poly(methyl methacrylate) (PMMA) to exploit high refractive and transparent organic–inorganic hybrid materials. Formation of TiO₂ particles of around 20 nm was conducted within hydrophilic core of block copolymer micelles of poly(methyl methacrylate‐block‐acrylic acid) (PMMA‐b‐PAA) in toluene via sol–gel process from titanium isopropoxide and hydrochloric acid. Subsequently, incorporation of TiO₂ particles into PMMA matrix was carried out by casting toluene solution of TiO₂ precursor‐loaded copolymer micelles, prepared from PMMA₃₅₀‐b‐PAA₉₃ and the precursor of mole ratio Ti⁴⁺/carboxyl 4.0, and PMMA. Hybrid films of TiO₂/PMMA exhibited high transparency to achieve transmission over 87% at 500 nm at 30 wt % of TiO₂ content. The refractive index of resulting hybrid films at 633 nm linearly increased with TiO₂ content to attain 1.579 at 30 wt % TiO₂, which was 0.1 higher than that of PMMA. Cross‐sectional transmission electron microscope images of TiO₂/PMMA hybrid films showed existence of TiO₂ clusters less than 100 nm, which were probably formed by aggregation or agglutination of TiO₂ particles during a drying process. It was also observed that decomposition temperature of the hybrid films elevated with increasing TiO₂ content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Light induced excited spin state trapping in the binuclear spin crossover compound [Fe(bpym)(NCS)2]2(bpym) exhibiting a high-spin ground state

A photo-magnetic effect is evidenced using near-infrared light in the binuclear complex [Fe(bpym)(NCS)₂]₂(bpym). This compound has a ⁵T_2g–⁵T_2g ground state and exhibits no thermal spin crossover – in contrast to the analogous [Fe(bpym)(NCSe)₂]₂(bpym). The estimated photo-conversion ratio is ca. 30%. By means of magnetic susceptibility measurements as well as Raman and infrared absorption spectroscopies, the nature of the photo-induced phase was established as the ⁵T_2g–¹A_1g state, which means that only one iron center is converted to low-spin. The photo-induced state was completely converted back to the ground state either by visible light excitation or by heating.     

Effects of ferrocenyl group on refractive index of colloidal crystal system formed by polymer-grafted silica in organic solvent

Colloidal crystallization of copolymer-grafted silica containing ferrocenyl groups in organic solvents and effects of ferrocenyl groups on effective refractive index of colloidal crystal systems were investigated. Poly(ferrocenyl metharylate (FeMA)-co-methyl methacrylate (MMA)-grafted silica gave colloidal crystallization in dimethylformamide and acetonitrile. The colloidal crystals exhibited characteristic coloration due to cooperative effects of specific absorption at 400–500 nm by ferrocenyl group and transmission of 700–800-nm light through the crystals. It was observed that effective refractive index of colloidal crystals systems of poly(FeMA-co-MMA)-grafted silica was higher than that of poly(MMA)-grafted silica. Normalized effective refractive index of the system linearly increased with mole fraction of FeMA in grafted copolymer. However, poly(FeMA-block-MMA) did not bring effective increase of the index because of bias formation of ferrocenyl group on silica.     

Synthesis of (1α)‐1,25‐Dihydroxyvitamin D3 with a β‐Positioned Seven‐Carbon Side Chain at C(12)

A convergent synthesis of an analogue of (1α)‐1,25‐dihydroxyvitamin D₃ ( 1b ) with a C₇ side chain at C(12), i.e., of 5 (Fig.), is described. A key step of the synthesis is the assembly of the triene system by a Pd^II‐catalyzed ring closure of an enol triflate (‘bottom’ fragment) followed by coupling of the resulting Pd^II intermediate with an alkenylboronate (‘upper’ fragment) (Scheme 2). The synthetic strategy allows isotopic labelling at the end of the synthesis.     

Intermediate as catalyst: catalytic asymmetric conjugate addition of nitroalkanes to α,β-unsaturated thioamides

Catalytic asymmetric conjugate addition of nitroalkanes to α,β-unsaturated thioamides is promoted by a mesitylcopper/(R)-DTBM-Segphos precatalyst, affording γ-nitrothioamides in moderate to high syn-selectivity and excellent enantioselectivity. The intermediate Cu-thioamide enolate functions as a soft Lewis acid/hard Br?nsted base cooperative catalyst to drive the catalytic cycle efficiently under proton transfer conditions.     

Giant Skyrmions stabilized by dipole-dipole interactions in thin ferromagnetic films

Motivated by a recent magnetization reversal experiment on a TbFeCo thin film, we study a topological excitation in the anisotropic nonlinear sigma model together with the Zeeman and magnetic dipole-dipole interactions. Dipole-dipole interactions turn a ferromagnet into a frustrated spin system, which allows a nontrivial spin texture such as a giant Skyrmion. We derive an analytic formula for the Skyrmion radius. The radius is controllable by the external magnetic field. It is intriguing that a Skyrmion may have already been observed as a magnetic domain. A salient feature is that a single Skyrmion can be created or destroyed experimentally. An analysis is made also on Skyrmions in chiral magnets.