Synthesis,crystal structure,and <Superscript>1</Superscript>H NMR spectra of a chloride-bridged chain complex of dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-<Emphasis Type="Italic">d</Emphasis><Subscript>5</Subscript>)benzoate

Deuterated dinuclear ruthenium(II,III) 3,4,5-tri(ethoxy-d ₅)benzoate, [Ru₂{3,4,5-(C₂D₅O)₃C₆H₂-COO}₄Cl] _n , was synthesized by a reaction of [Ru₂(C₂H₅COO)₄Cl] _n and 3,4,5-tri(ethoxy-d ₅)benzoic acid and characterized by single-crystal X-ray analysis as well as IR, UV-VIS, and ¹H NMR spectra, and compared with those of the undeuterated complex [Ru₂{3,4,5-(C₂H₅O)₃C₆H₂COO}₄Cl] _n . Single-crystal X-ray analysis showed that chloride ligands bridge the dinuclear ruthenium(II,III) units at the axial positions to form a zigzag chain molecule with the Ru¹-Cl-Ru² angle of 123.82(4)°. ¹H NMR spectra in CD₂Cl₂ displayed a broad signal attributable to o-H atoms on the phenyl rings of the benzoate ligands from approximately δ = 23 to δ = 32 at 25°C and several signals from approximately δ = −50 to δ = 50 at −80°C. These spectra show the preservation of the polymeric or oligomeric chain structure in dichloromethane, which is supported by the solution behavior confirmed by the UV-VIS spectra and electronic conductance.     

Enantioselective total synthesis of octalactin a using asymmetric aldol reactions and a rapid lactonization to form a medium-sized ring

Octalactin A, an antitumor agent containing an eight-membered lactone moiety, has been stereoselectively prepared by means of enantioselective aldol reactions of selected silyl enolates with achiral aldehydes, promoted by a chiral Sn(II) complex. The medium-sized lactone part was effectively constructed by way of a new and rapid mixed-anhydride lactonization using 2-methyl-6-nitrobenzoic anhydride (MNBA) with a catalytic amount of 4-(dimethylamino)pyridine (DMAP) or 4-(dimethylamino)pyridine 1-oxide (DMAPO). The use of only 5 mol % of DMAP or 2 mol % of DMAPO rapidly promoted formation of the medium-sized ring of the octalactin, demonstrating the remarkable efficiency of the new lactonization protocol.     

Stable oscillations of a spatially chaotic wave function in a microstadium laser

Laser action on a single spatially chaotic wave function is obtained as a final stable state in a nonlinear dynamical model of a stadium shaped resonant cavity with an active medium. The stable single-mode lasing state corresponds to a particular metastable resonance of the cavity which wins a competition among multiple modes with positive net linear gain and has a distinct lasing threshold.     

Two-Dimensional Multi-Lens Array with Circular Aperture Spherical Lens for Flat-Top Irradiation of Inertial Confinement Fusion Target

A two-dimensional multi-lens array 350 mm in diameter with spherical element lenses has been tested to improve the irradiation uniformity of a high power glass laser for inertial confinement fusion (ICF). A circular shape for the element lens aperture is chosen to eliminate azimuthally asymmetric intensity distribution. An approximate flat-top intensity distribution is obtained with a lens array of 37 lenses. Beam patterns of a coherent laser and partially coherent light (PCL) with the random phase plate (RPP) and the multi-lens array (MLA) are measured in a GEKKO XII glass laser system. Spherical mode structure of the irradiation nonuniformity of 5.6% with MLA is estimated with cos3 θ distribution of absorption coefficient in the target plasma.     

Anticorrelated bidirectional output of quasistadium-shaped semiconductor microlasers

Time-domain properties of the output from quasistadium-shaped microcavity semiconductor lasers are studied. Ring modes generating a bidirectional output are selectively excited by partial pumping. We observe a high anticorrelation between the two beams output from the ring modes. This can be considered as the generalization of alternate oscillations reported previously. We find that the outputs exhibit a robust slow modulation of 4–10 MHz, and explain it by the quasi-degeneracy of the resonator modes.     

Universal Single-Mode Lasing in Fully Chaotic Billiard Lasers

By numerical simulations and experiments of fully chaotic billiard lasers, we show that single-mode lasing states are stable, whereas multi-mode lasing states are unstable when the size of the billiard is much larger than the wavelength and the external pumping power is sufficiently large. On the other hand, for integrable billiard lasers, it is shown that multi-mode lasing states are stable, whereas single-mode lasing states are unstable. These phenomena arise from the combination of two different nonlinear effects of mode-interaction due to the active lasing medium and deformation of the billiard shape. Investigations of billiard lasers with various shapes revealed that single-mode lasing is a universal phenomenon for fully chaotic billiard lasers.     

First Isolation and Characterization of the Highly Coordinated Group 14 Enolates: Effects of the Coordination Controls on the Geometry and Tautomerization of Germyl Enolates

The Group 14 enolates play an important part in many organic reactions. Herein, the reduction of an α‐bromo ketone with germanium(II) salts cleanly afforded the corresponding germyl enolate as an isolatable species. This experimental reductive generation of a germyl enolate enabled us to characterize both C‐ and O‐bound tautomers derived from an identical precursor and to unveil the tautomeric mechanisms, including the kinetic parameters and the relative stability of these tautomers, along with confirmation from DFT calculations. Moreover, the highly coordinated germyl enolates were isolated by a stabilization process induced by adding ligands. All products were characterized by NMR spectroscopy and X‐ray crystallography.     

Synthesis and magnetic properties of polymeric complexes containing ruthenium(II)-ruthenium(III) tetracarboxylato units linked by cyanato,thiocyanato, and selenocyanato ligands

Polymeric complexes of ruthenium(II)-ruthenium(III) tetracarboxylato units linked by cyanato, thiocyanato, and selenocyanato ligands [Ru₂{O₂C(CH₂)_mCH₃}₄(L)] _n (m = 0, 4–7; L = OCN⁻, SCN⁻, and SeCN⁻) were prepared and characterized based on the elemental analyses, IR, and diffuse reflectance spectra. Magnetic susceptibilities were measured at the temperature range of 4.5 K to 300 K, where the interdimer antiferromagnetic interactions were revealed. The strongest interaction was exhibited in case of m = 7 and L = OCN⁻. ¹H-NMR spectra of [Ru{O₂C(CH₂)₇CH₃}₄(SCN)] _n in CD₂Cl₂ showed broad signals which can be ascribed to polymeric species, as the addition of tetrabutylammonium thiocyanate caused sharper signals due to the formation of [Ru₂{O₂C(CH₂)₇CH₃}₄(SCN)₂]⁻ adduct as the main species in the solution. Dedicated to Professor Milan Melník on the occasion of his 70th birthday     

Formation mechanism of one-dimensional Si islands on a H/Si(001) surface

The formation mechanism of one-dimensional Si islands on a H/Si(001)-(2x1) surface is studied using scanning tunneling microscopy/spectroscopy and first-principles calculations. We observed that one-dimensional islands that are made from dimer chains are formed at the initial growth stages similar to the bare Si(001) surface. It is found that the number of odd-numbered dimer chains is larger than that of even-numbered dimer chains. We propose the growth processes of the two types of growth edges to explain the observation.