Structures of 17,19-hexatriacontadiyne monolayers on Au(111) studied by infrared reflection absorption spectroscopy and scanning tunneling microscopy

The aggregation and reaction of 17,19-hexatriacontadiyne molecules are studied on a Au(111) surface. The molecular orientation and arrangement are elucidated by infrared reflection absorption spectroscopy (IRAS) and scanning tunneling microscopy (STM). A vapor-deposited monolayer and a multilayered film formed by adsorption from the solution provide IRA spectra with bands due to the antisymmetric and symmetric stretching of methylenes in the gauche conformation. After the adsorbed film is rinsed with the solvent, however, the spectrum loses the gauche bands and is characterized by the enhanced C-H(distal) and C-H(proximal) stretching bands, which means that all-trans molecules are laid flat. Only STM images for the rinsed film display columnar structures on the herringbones of the reconstructed Au(111) surface; the alkyl chain direction is found to be parallel to the Au atom row. The results indicate that an ordered monolayer is formed first at the liquid-solid interface, and then, disordered overlayers with the gauche conformation are grown but removed by a rinse. Upon exposure to UV light, thus obtained monomer columns are converted into oligomers with flexible backbones and an increased gauche population in the alkyl chains, which resemble red phase polydiacetylenes in LB films.     

Catalytic asymmetric epoxidation of alpha,beta-unsaturated esters using an yttrium-biphenyldiol complex

We succeeded in a catalytic asymmetric epoxidation reaction of alpha,beta-unsaturated esters via a conjugate addition of an oxidant using 2-10 mol % of the yttirium-chiral biphenyldiol catalyst. A variety of substrates with beta-aryl and beta-alkyl substituents were epoxidized efficiently, yielding the corresponding alpha,beta-epoxy esters in up to 97% yield and 99% ee.     

Incoherent quasielastic neutron scattering study on the polymorphism of tristearin: dynamical properties of hydrocarbon chains

Dynamical properties of acyl chains in the three polymorphic phases alpha, beta', and beta of tristearin [C(3)H(5)(OCOC(17)H(35))3] have been studied by means of incoherent quasielastic neutron scattering (IQNS) using selectively deuterated samples. The mean square displacement of hydrogen atoms, , was estimated from the scattering vector Q dependence of the elastic scattering component under the harmonic approximation. It was shown that the temperature dependence of was significantly different between the three phases. There was no marked difference in between these phases up to 193 K, and the value increased linearly with temperature. Although the beta phase remained linear up to 293 K, the alpha and beta' phases started to show a nonlinear increase around 200 K, suggesting an anharmonic nature of molecular motions. The alpha phase exhibited the most conspicuous temperature dependence. These characteristics were ascribable to the difference in the lateral packing of acyl chains. Compared with the beta phase which has a tightly packed T// subcell, the beta' and alpha phases have looser O perpendicular and H subcells, respectively. The molecular motion in the alpha phase was analyzed using the model of uniaxial rotational diffusion in a onefold cosine potential. It has been clarified that the rotational fluctuation about the chain axis in the alpha phase is rather restricted compared with that in the rotator phase of n-alkanes.     

Nona-coordinated chiral Eu(III) complexes with stereoselective ligand-ligand noncovalent interactions for enhanced circularly polarized luminescence

Circularly polarized luminescence (CPL) of chiral Eu(III) complexes with nona- and octa-coordinated structures, [Eu(R/S-iPr-Pybox)(D-facam)(3)] (1-R/1-S; R/S-iPr-Pybox, 2,6-bis(4R/4S-isopropyl-2-oxazolin-2-yl)pyridine; D-facam, 3-trifluoroacetyl-d-camphor), [Eu(S,S-Me-Ph-Pybox)(D-facam)(3)] (2-SS; S,S-Me-Ph-Pybox, 2,6-bis(4S-methyl-5S-phenyl-2-oxazolin-2-yl)pyridine), and [Eu(Phen)(D-facam)(3)] (3; Phen, 1,10-phenanthroline) are reported, and their structural features are discussed on the basis of X-ray crystallographic analyses. These chiral Eu(III) complexes showed relatively intense photoluminescence due to their (5)D(0) → (7)F(1) (magnetic-dipole) and (5)D(0) → (7)F(2) (electric-dipole) transition. The dissymmetry factors of CPL (g(CPL)) at the former band of 1-R and 1-S were as large as -1.0 and -0.8, respectively, while the g(CPL) of 3 at the (5)D(0) → (7)F(1) transition was relatively small (g(CPL) = -0.46). X-ray crystallographic data indicated specific ligand-ligand hydrogen bonding in these compounds which was expected to stabilize their chiral structures even in solution phase. CPL properties of 1-R and 1-S were discussed in terms of transition nature of lanthanide luminescence.     

Iron-catalyzed sulfonyl radical formations from sulfonylhydrazides and oxidative addition to alkenes

Generation of sulfonyl radicals from sulfonylhydrazides has been achieved in the presence of a non-toxic iron catalyst and oxygen. The intermolecular addition of resultant sulfonyl radicals to alkenes affords β-hydroxysulfone compounds.     

Three-dimensionally arrayed and mutually connected 1.2-nm nanopores for high-performance electric double layer capacitor

Zeolite-templated carbon is a promising candidate as an electrode material for constructing an electric double layer capacitor with both high-power and high-energy densities, due to its three-dimensionally arrayed and mutually connected 1.2-nm nanopores. This carbon exhibits both very high gravimetric (140-190 F g(-1)) and volumetric (75-83 F cm(-3)) capacitances in an organic electrolyte solution. Moreover, such a high capacitance can be well retained even at a very high current up to 20 A g(-1). This extraordinary high performance is attributed to the unique pore structure.     

From tetragermacyclobutene to tetragermacyclobutadiene dianion to tetragermacyclobutadiene transition metal complexes

The reaction of 3,4-dichlorotetragermetene derivative 2 with Na(2)[Fe(CO)(4)] in THF produced a (tetragermacyclobutadiene)tricarbonyliron complex, [{η(4)-((t)Bu(2)MeSi)(4)Ge(4)}]Fe(CO)(3)4, which has a slightly folded Ge(4) ring perhaptocoordinated to the Fe center. Structural and spectral characteristics of 4 show a remarkable π-donating ability of the tetragermacyclobutadiene ligand toward the transition metal, surpassing that of tetrasilacyclobutadiene and cyclobutadiene ligands. Reduction of 2 with KC(8) resulted in exclusive formation of the dipotassium salt of the tetragermacyclobutadiene dianion derivative 3(2-)·[K(+)(thf)(2)](2), representing a rare example of a 6π-electron compound that, on the basis of its structural and magnetic properties, was recognized as a nonaromatic species. Reaction of 3(2-)·[K(+)(thf)(2)](2) with CpCoI(2)(PPh(3)) produced a (cyclopentadienyl)(tetragermacyclobutadiene)cobalt complex, [{η(4)-((t)Bu(2)MeSi)(4)Ge(4)}]CoCp 7, as the first example of a sandwich compound featuring an all-germanium-containing cyclic polyene ligand.     

Tubular structures bearing channels in organic crystals composed of adamantane-based macrocycles

Five macrocyclic molecules (1–5) were efficiently synthesized from the dimerization and trimerization of di-substituted adamantane derivatives, which were composed of three different aromatic units and two different linker groups. Three single-crystals were obtained from these macrocyclic molecules, including a set of pseudopolymorphs (3a and 3b) of macrocycle 3 and another macrocycle 5 (5a). Single crystal X-ray analysis revealed that the three monocyclic compounds were rectangular or square in shape with solvent molecules in the cavity. Macrocycle 3 in 3a formed stacks to produce tubular structures with channels that assembled into three-dimensional networks through CH/π interactions.