Structure and magnetic properties of the two-dimensional ferrimagnet (NEt4)[[Mn(salen)]2Fe(CN)6]: investigation of magnetic anisotropy on a single crystal

The title compound, (NEt(4))[[Mn(salen)](2)Fe(CN)(6)] (1), was synthesized via a 1:1 reaction of [Mn(salen)(H(2)O)]ClO(4) with (NEt(4))(3)[Fe(CN)(6)] in a methanol/ethanol medium (NEt(4)(+) = tetraethylammonium cation, salen(2)(-) = N,N'-ethylenebis(salicylidene)iminate). The two-dimensional layered structure of 1 was revealed by X-ray crystallographic analysis: 1 crystallizes in monoclinic space group P2(1)/c with cell dimensions of a = 12.3660(8) A, b = 15.311(1) A, c = 12.918(1) A, beta = 110.971(4) degrees, Z = 2 and is isostructural to the previously synthesized compound, (NEt(4))[[Mn(5-Clsalen)](2)Fe(CN)(6)] (5-Clsalen(2-) = N,N'-ethylenebis(5-chlorosalicylidene)iminate; Miyasaka, H.; Matsumoto, N.; Re, N.; Gallo, E.; Floriani, C. Inorg. Chem. 1997, 36, 670). The Mn ion is surrounded by an equatorial salen quadridentate ligand and two axial nitrogen atoms from the [Fe(CN)(6)](3-) unit, the four Fe[bond]CN groups of which coordinate to the Mn ions of [Mn(salen)](+) units, forming a two-dimensional network having [[bond]Mn[bond]NC[bond]Fe[bond]CN[bond]](4) cyclic repeating units. The network is spread over the bc-plane of the unit cell, and the layers are stacked along the a-axis. The countercation NEt(4)(+) is located between the layers. Compound 1 is a ferrimagnet with T(c) = 7.7 K and exhibits hysteresis with a remnant magnetization of 13.44 cm(3).mol(-1) (M/N mu(B) = 2.4) at zero field and a coercivity of 1000 Oe when the powder sample was measured at 1.9 K. Magnetic measurements of a direction-arranged single crystal were also carried out. The orientation of the crystallographic axes of a selected single crystal was determined by X-ray analysis, and magnetization was measured when an external field was applied in the a*, b, and c directions. The magnetization in the a* direction increased more easily than those in the b and c directions below the critical temperature. No hysteresis was observed only for the measurement in the a* direction, indicating the presence of strong structural anisotropy with potential anisotropy on Mn(III) ions.     

Dual activation in a homolytic coupling reaction promoted by an enantioselective dinuclear vanadium(IV) catalyst

A new concept of dual activation catalysis in homolytic coupling reaction of 2-naphthol derivatives is described. The dinuclear vanadium(IV) catalyst (R,S,S)-1a promotes the oxidative coupling reaction of 2-naphthol derivatives with high reactivity and enantioselectivity. This dual activation mechanism is supported by the fact that the reaction rate of oxidative coupling of 2-naphthol promoted by the (R,S,S)-1a is 48 times faster than that of the mononuclear complex (S)-3 and a lower catalyst loading of (R,S,S)-1a shows higher catalyst efficiency both in enantioselectivity and chemical yield.     

Efficient Light-Harvesting Antennae Resulting from the Dense Organization of Dyes into DNA Junctions through d-Threoninol

Herein we report the construction of efficient light-harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d -threoninol. Six pyrene donors could be incorporated into each arm without self-quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three- to eight-way junctions were systematically compared. Six- and eight-way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even-numbered junctions had higher efficiencies than odd-numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems.     

The synthesis and reaction of N-sulfenyl heterocycles: development of effective sulfenylating reagents

Various N-sulfenyl heterocycles were synthesized by transamination of sulfenamides using a chlorine gas-free method. The N-sulfenyl heterocycles behaved as sulfenylating reagents of anilines; N-sulfenylbenzimidazoles were the most effective.     

Synthesis and characterization of phosphorous-bridged bisphenoxy titanium complexes and their application to ethylene polymerization

Phosphorous-bridged bisphenoxy titanium complexes were synthesized and their ethylene polymerization behavior was investigated. Bis[3-tert-butyl-5-methyl-2-phenoxy](phenyl)phosphine tetrahydrofuran titanium dichloride (4a) was obtained by treatment of 3 equiv of n-BuLi with bis[3-tert-butyl-2-hydroxy-5-methylphenyl](phenyl)phosphine hydrochloride salt (3a) followed by TiCl₄(THF)₂ in THF. THF-free complexes 5a-5d were synthesized more conveniently by the direct reaction of MOM-protected ligands (2a-2d) with TiCl₄ in toluene. X-ray analysis of 4a revealed that the ligand is bonded to the octahedral titanium (IV) center in a facial fashion and two chlorine atoms possess cis-geometry. Complexes 4a and 5a-5d were utilized as catalyst precursors for ethylene polymerization. Complex 5c gave high molecular weight polyethylene (M_w = 1,170,000, M_w/M_n = 2.0) upon activation with Al(ⁱBu)₃/[Ph₃C][B(C₆F₅)₄] (TB). Ethylene polymerization activity of 5d activated with Al(ⁱBu)₃/TB reached 49.0 × 10⁶ g mol (cat) ⁻¹ h⁻¹.     

Total synthesis of (-)-tuberostemonine

The first total synthesis of the complex pentacyclic Stemona alkaloid tuberostemonine was accomplished in 24 steps and in 1.4% overall yield from a hydroindole intermediate which is readily obtained in three steps from Cbz-l-tyrosine. An innovative synthetic strategy was applied that relays the single stereocenter of the amino acid precursor into nine of the ten stereogenic carbons of the target molecule. Among the highlights of the synthetic methodology are the 3-fold use of ruthenium catalysis, first in an azepine ring-closing metathesis and then in an alkene isomerization followed by a cross-metathesis propenyl-vinyl exchange, as well as the stereoselective attachment of the gamma-butyrolactone moiety to the core tetracycle by use of a lithiated ortho ester.     

Molecular Design for Reversing the Photoswitching Mode of Turning ON and OFF DNA Hybridization

A new photoswitch for DNA hybridization involving para‐substituted azobenzenes (such as isopropyl‐ or tert‐butyl‐substituted derivatives) with L ‐threoninol as a linker was synthesized. Irradiation of the modified DNA with visible light led to dissociation of the duplex owing to the destabilization effect of the bulky substituent on the trans‐azobenzene. In contrast, trans‐to‐cis isomerization (UV light irradiation) facilitated duplex formation. The direction of this photoswitching mode was entirely reversed relative to the previous system with an unmodified azobenzene on D ‐threoninol whose trans form turned on the hybridization, and cis form turned it off. Such reversed and reversible photoswitching of DNA hybridization was directly demonstrated by using fluorophore‐ and quencher‐attached oligonucleotides. Furthermore, it was revealed that the cis‐to‐trans thermal isomerization was greatly suppressed in the presence of the complementary strand owing to the formation of the more‐stable duplex in the cis form.     

Mesoporous TiO2 core-shell spheres composed of nanocrystals with exposed high-energy facets: facile synthesis and formation mechanism

A facile new method that combines electrospray and hydrothermal treatment is used to prepare mesoporous core-shell TiO(2) spheres with high specific surface areas and high pore volumes. Interestingly, the resulting TiO(2) spheres are composed of anatase TiO(2) nanocrystals with exposed step-like {001} and smooth {010} facets. The percentage of exposed {001} facets can be adjusted by changing the experimental parameters used in the electrospray and hydrothermal treatment processes, such as the contents of poly(N-vinyl-2-pyrrolidone) and acetic acid. The combination of high specific surface area (>100 m(2) g(-1)), high pore volume (>0.30 cm(3) g(-1)), useful pore size (10-15 nm), spherical core-shell structure, and exposed high energy facets makes these TiO(2) spheres an important candidate for use in many photoelectrochemical applications. The formation mechanism of the mesoporous TiO(2) spheres is also studied. The great advantage of this method is that interesting and complicated mesoporous superstructures can be prepared using electrospray technology.     

Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H₂MoO₄) dissolved in 2.82% hydrofluoric acid (HF) and H₃BO₃ as precursors. The crystal was found to belong to a hexagonal hydrate system MoO₃.nH₂O (n~0.56). The unit cell lattice parameters are a=10.651 Å, c=3.725 Å and V=365.997 Å³. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectra showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo⁶⁺ oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 °C, the hexagonal MoO₃.nH₂O was transformed into the thermodynamically stable orthorhombic phase.     

Crystal-face dependence and photoetching-induced increases of dye-sensitized photocurrents at single-crystal rutile TiO2 surfaces

Dye-sensitized photocurrents at (100)-, (001)-, and (110)-cut TiO(2) rutile surfaces were increased by photoetching of TiO(2), but the increasing ratio strongly depended on the cut crystal faces and the illumination intensity for the photoetching. For the (110)-cut surface, the photocurrent increase was moderately large and in proportion to the increase in the surface area of TiO(2) induced by the photoetching, irrespective of the illumination intensity for the photoetching. On the other hand, the photocurrent increases for the (001)- and (100)-cut surfaces, especially that for the (001)-cut surface, were prominent and largely exceeded the increases in the surface area. The results were explained by taking into account the following factors: (1) The (001)- and (100)-cut surfaces were thermodynamically unstable in contrast to the (110)-cut surface and had thicker inactive surface layers (or higher densities of surface defects), produced by surface reconstruction during heat treatment of TiO(2) at 550 degrees C in a hydrogen atmosphere for getting n-type semiconductivity. (2) Photoetching not only increased the surface area through formation of nanoholes and grooves at the surface but also effectively removed the thin inactive surface layers (or surface defects).