AbstractThe Title Research Articles

Rhodium-catalyzed Addition of Organo[2-(hydroxymethyl)phenyl]dimethylsilanes to Arenesulfonylimines

Abstract The title reaction is found to proceed in the presence of a rhodium/diene catalyst. Variously substituted diarylmethylamines and allylamines having an N-arenesulfonyl protection are obtained in good yields, which are important building blocks in organic synthesis.

RE2+xI2M2+y (RE = Ce,Gd, Y; M = Al, Ga): Reduced Rare Earth Halides with a Hexagonal Metal Atom Network

Abstract The title compounds were synthesized from RE, REI3 (RE = Ce, Gd, Y) and Al or Ga under an Ar atmosphere at 930 - 950 °C. The non-stoichiometric Ce2+xI2Al2+y and Ce2+xI2Ga2+y compounds crystallize in the space group R3̄m (No. 166) with lattice constants a = 4.3645(3), c = 35.914(2) Å for the Al and a = 4.3009(2), c = 35.680(4) Å for the Ga compound. Excess electron density found in the Wyckoff position 3a could be due to a fractional occupation by Ce or M (x = 0.06, y = 0 or x = 0, y = 0.11 in the case of the Ga compound). The stoichiometric Gd2I2Ga2 and Y2I2Ga2 compounds crystallize in the space group P3̄m1 (No. 164) with lattice constants a = 4.1964(1) and 4.1786(7) Å , c = 11.4753(4) and 11.434(2) Å , respectively. Their structures feature M-centered (M = Al, Ga) RE trigonal prisms condensed via common rectangular faces. The electronic origin of the surplus of metal atoms in the octahedral voids between the I-layers of the Ce compounds was explored via extended Hückel-type calculations. Magnetic susceptibility, electrical resistivity and heat capacity measurements have also been carried out. These reveal a metal-insulator transition of Gd2I2Ga2 at 40 K.

Cross-coupling Reaction of Allylic and Benzylic Carbonates with Organo[2-(hydroxymethyl)phenyl]dimethylsilanes

Abstract The title reaction is found to proceed in the presence of a palladium catalyst and in the absence of any activator. Various functional groups are tolerated to give a diverse range of 1,4-diene and diarylmethane products, which are ubiquitous units of natural products and pharmaceuticals.

5H,13H-5,13a-[1′,2′]Benzenocyclopenta[rst]pentaphen-13-one: A New Triptycene Derivative with a Strained Structure

Abstract The title compound, a new anthracene-containing triptycene derivative, was synthesized. The crystal structure shows its strained configuration and intermolecular π–π stacking arrangement. Photochemical [4 + 4] dimerization occurs easily in solution and in the solid state, even under visible-light irradiation.

Cu2(C3H2N3O3)2(C10H8N2): A Hydrogen-bonded Assemblies Supermolecule Containing 1D Channels and Novel Two-coordinated Linear N–Cu–N Configurations

Abstract The title compound was successfully synthesized by the simple hydrothermal route. Interestingly, the title compound exhibits a rare two-coordinated linear N–Cu–N configuration around cuprous ions. Furthermore, the title compound is stacked via hydrogen-bond assembly in three dimensions to form the supermolecule with a channel of 3.98(5) × 8.81(1) Å along the b axis, which may be useful in studying the porous coordination materials.

Synthesis and characterization of Na2Ba4Ga2Sb6 and Li13Ba8GaSb12

Abstract The title compounds were synthesized from the elements by heating the corresponding stoichiometric mixtures at high temperature. Their structures were determined from single-crystal X-ray diffraction. Na2Ba4Ga2Sb6 (Pnma, Z = 8, a = 12.3468(10) Å, b = 10.6621(10) Å, c = 13.8344(10) Å) contains chains of ∞[Ga2Sb6]10–. The repeating unit is made of an edge-sharing Ga-centered tetrahedron GaSb2(μ-Sb)2 and another Ga-centered tetrahedron but with additional antimony that is exo-bonded to one of the corners forming Sb–Sb dumbells, i.e. GaSb(Sb–Sb)(μ-Sb)2. The unit connects to neighboring units via sharing two corners of the tetrahedra, i.e. [Ga2Sb5Sb2/2]. Li13Ba8GaSb12 (C2/m, Z = 2, a = 18.0650(10) Å, b = 4.9407(10) Å, c = 13.0123(10) Å, β = 126.728(10)°) contains three different types of anions: single-atom anions of Sb3–, dumbells of Sb4–, and isolated Ga-centered tetrahedra of GaSb4 9–. The two compounds are electronically balanced, and this is confirmed by four-probe conductivity and magnetic measurements. Their very narrow band gaps, 0.014 and 0.049 eV for Na2Ba4Ga2Sb6 and Li13Ba8GaSb12, respectively, make them potential thermoelectric materials.

The Beat of the Land: Place and Music in Tim Winton’s Dirt Music

Abstract The title of Tim Winton’s 2001 novel Dirt Music reveals one of the central binaries at work within: Dirt, or place, presence, nature on the one hand, and Music, or emotions, past, culture on the other. Dirt Music, set in Western Australia, revolves around the love story between Georgie Jutland and Lu(ther) Fox. Lu, a folk guitarist, retreats from society after the tragic death of his family, who also formed his band. During his stay in the deserted North Australian coastal region, he experiments with the possibilities of living - and making music - outside of cultural constraints. The emphasis in this paper will be on how the two factors of dirt and music interplay within the construction of his identity. The novel proposes a perspective on music that eventually offers a reconciliation of the alienation of man’s identity between nature and culture.

Chemistry of Anthracene–Acetylene Oligomers. II. Synthesis, Structure, and Properties of 1,8-Anthrylene–Ethynylene Cyclic Tetramers and Related Acyclic Oligomers

Abstract The title π-conjugated oligomers consisting of anthracene and acetylene units were synthesized to construct a new type of three-dimensional organic architecture. An acyclic chain was extended by the sequence of the Sonogashira coupling and the desilylation from 1,8-diethynylanthracene derivatives and 1,8-diiodoanthracene to form a tetramer, which was then coupled intramolecularly to afford a cyclic tetramer as orange crystals. It is characteristic that a substituent free cyclic tetramer shows the hypochromic effect in the UV spectrum and the presence of an excimer-type emission in the fluorescence spectrum. X-ray analysis revealed that the cyclic tetramer took a diamond prism structure of nearly C2 symmetry, and the skeletal swing between the two enantiomeric forms via a square prism form was observable by dynamic NMR spectroscopy (barrier: ca. 38 kJ mol−1). The structural and spectral properties as well as some reactivities of the cyclic tetramer and related acyclic oligomers up to heptamer are reported.

Synthesis and Carrier-transporting Properties of 5,10-Dihydro-5,5-dimethyl-10,10-diphenyl-1,9-diazasilanthrene

Abstract The title compound was synthesized and investigated as an electron-transporting and hole-blocking material for an organic electroluminescent (EL) device. EL efficiency of the phosphorescent device indicated a good performance of the hole-blocking ability of the compound. The maximum external quantum efficiency was recorded as 14.9% at a low current density of 0.03 mA cm−2.

Formation and Nonlinear Optical Properties of a Novel Polymeric Cadmium(II) Complex Bridged by Sulfur Ions

Abstract The title coordination polymer, [Cd(NH2NHCSNH2)(HS)2]n·nH2O, has been obtained by self-assembling from the reaction of a methanol/water (volume ratio, 1/1) solution containing cadmium chloride with equivalent amount of succinic acid and thiosemicarbazide. The X-ray crystal analysis reveals that the cadmium atoms are bridged by HS− ligands and mutual sulfur atoms which contribute to formation of the infinite one-dimensional (1D) inorganic–organic chain in a zig-zag way. The second harmonic generation (SHG) response of the complex is much stronger than that of urea.

Application of N,N,N′,N′-Tetrasubstituted 1,3-Bis(4-aminophenyl)azulenes to Hole-injecting Materials for Durable Organic EL Devices without Color Fade

Abstract The title 1,3-bis(aminophenyl)azulenes were synthesized from 1,3-dihaloazulene in two steps involving the Suzuki cross-coupling with 4-bromophenylboronic acid and subsequent Pd-catalyzed amination. Their HOMO energy levels were estimated to be comparable to that of the widely used hole-injecting (HI) material, copper phthalocyanine. The application of these diamines to HL materials in organic electroluminescent (EL) devices was also studied as non-cyanine and non-polyamine substance.

Cis-trans-cis-Tetrabromotetramethylcyclotetrasiloxane: a Versatile Precursor of Ladder Silsesquioxanes

Abstract The title compound was isolated for the first time by a novel procedure including dephenylbromination of cyclotetrasiloxane. The stereostructure of the tetrabromide was confirmed by condensation with diphenylsilanediol, affording anti-tricyclo[7.3.1.13,7]hexasiloxane. This tetrabromide spontaneously decomposed in air to afford a white powder insoluble in organic solvents. Measurements of the TG, IR, and solid-state NMR spectra of the product revealed that a ladder polysilsesquioxane with high thermal stability and stereoregularity was obtained.

On the crystal structure of γ-AgMg4

Abstract The title compound with the trivial name γ-AgMg4 is obtained by melting the elements in weld-sealed tantalum ampoules and subsequent annealing. The alloys were characterized by chemical, metallographic, thermal and X-ray powder analyses. γ-AgMg4 is formed by a peritectoid reaction at 472(2) °C from ɛ′-Ag17Mg54 and δ-(Mg). The exact composition corresponds to the formulas AgMg4.08 or Ag9Mg36.7 with 80.3(1) at-% Mg concentration. The title compound is a complex metallic alloy phase due to the large number of atoms and intrinsic structural disorder. γ-AgMg4 crystallizes hexagonal in the space group P63/m with a = 12.4852(8) Å and c = 14.4117(9) Å in a unique structure type without a perceptible homogeneity range. The crystal structure has been studied including disorder phenomena by means of Rietveld refinements of X-ray and neutron powder diffraction data and X-ray single crystal structure analyses. The crystal structure is a hitherto unknown I3 cluster phase, i.e., an intermetallic compound with building blocks of three vertex connected icosahedra as the fundamental structural units joined via a small number of connection types (here B- and L-type). Channels along [001] reveal distinct structural disorder described as a packing of approximately 1.9 icosahedra, 1.3 tricapped trigonal prisms and 0.4 Frank-Kasper Z15 polyhedra per unit cell. The findings support the usefulness of the I3 cluster concept as a construction kit concerning not only simple subunits but also more complex “patches” with inherent structural disorder.

Application of the carbene cyclization-cycloaddition cascade in total synthesis

Abstract The title reaction is a key transformation that has been applied to the synthetic studies of the antitumor and antifungal compounds, the pseudolaric acids.

A Novel Crown-Ether Stabilized Oxonium Halogenochalcogenate(IV): [H7O3(Bis-dibromo-dibenzo-30-crown-10)][Se2Br9]·1.5CH2Cl2

Abstract The title compound [H7O3(bis-dibromo-dibenzo-30-crown-10)][Se2Br9] ·1.5CH2Cl2 (1) was isolated from a solution of SeBr4 and dibenzo-30-crown-10 in CH3CN/CH2Cl2 containing a small amount of hydrobromic acid. During the reaction the crown ether is brominated by HBr. The compound crystallizes in the monoclinic space group P21/n with a = 17.688(11), b = 14.921(6), c = 20.521(12) Å , β = 97.71(5)°, and Z = 4. 1 is a novel example in the series of supramolecular halogenochalcogeno acids prepared in our group in which different oxonium cations are stabilized and encapsulated by crown ethers. Especially in this class of superacids complexation by cyclic polyethers offers covenient and variable possibilities for the controlled synthesis of oxonium cations. In the present case the large dibenzo-30-crown-10 ring systems are able to stabilize trinuclear [H7O3]+ cations within their cavities. Besides the macromolecular cations and some dichloromethane solvent molecules, the crystal structure of 1 contains molecular [Se2Br9]− ions with approximate D3h symmetry, each consisting of two face-sharing SeBr6 octahedra.

One-Pot Synthesis of 12-Hydroxy-12H-benzo[b]thioxanthene-6,11-diones from 1,4-Naphthoquinone and o-Acylbenzenethiols

Abstract The title benzo[b]thioxanthenequinone derivatives could be prepared in one-pot via a sequential conjugate addition and an aldol-type reaction between 1,4-naphthoquinone and o-acylbenzenethiols, followed by oxidation with 1,4-naphthoquinone or air.

A New Ternary Arsenide LaNi5As3: Preparation and Crystal Structure

Abstract The title compound was prepared from the elements by arc-melting followed by annealing in silica tubes at 1070 K for 3 months. The orthorhombic structure of LaNi5As3 was solved and refined from X-ray single crystal data: space group Pnma, a = 11.179(2), b = 3.9133(5), c = 24.443(3) Å , Z = 8, R = 0.040, Rw = 0.039 for 1045 unique reflections with I > 2σ (I) and 110 parameters. It is a new structure type, which can be described by condensed units of trigonal prisms around the arsenic atoms linked together to infinite zigzag chains. The structural features of LaNi5As3 are discussed in comparison with some representatives of a large family of structures with a metal/non-metal ratio equal or close to 2:1.

Novel Donor–π–Acceptor Compounds Containing 1,3-Dithiol-2-ylidene and Tetracyanobutadiene Units

Abstract The title donor–π–acceptor compounds were prepared by the reaction of acetylenes containing a 1,3-dithiol-2-ylidene unit with tetracyanoethylene (TCNE). They showed amphoteric properties and intramolecular charge-transfer absorptions in the visible region. The molecular and crystal structures were revealed by X-ray analysis.

The Synthesis, Crystal Structure and Spectroscopic Properties of a Dinuclear μ–Pyrazolato–N,N’–Bridged Dinickel(II) Complex of 1,3–Bis(salicylideneamino)propan–2–ol

Abstract The title compound [Ni2(L)(3,5 prz)], prz = pyrazolate with the formally pentadentate ligand L = 1,3-bis(salicylideneamino)propan-2-olate, was synthesized and identified using elemental analysis and IR spectroscopy. It crystallizes in the monoclinic space group P21/c with cell parameters a = 29.873(4), b = 11.131(2), c = 13.166(3) Å , β = 107.770(10)°, V = 4169.0(13) Å3, Z = 4, Dcal = 1.618 Mg/m3. The nickel ions are bridged by the alkoxo group of the ligand and the N atoms of the μ-pyrazolate group. Each nickel(II) ion is coordinated by two N atoms and two O atoms, forming a square with trans-N2O2 geometry. The Ni···Ni distance and the Ni−O−Ni angle are 3.371(1) Å and 126.4(1)°, respectively.

A Novel Photosensitizer of Palladium(II) Phthalocyanine Tetrasulfonate for Chlorophenol Oxidation under Visible Light Irradiation

Abstract The title complex has been found to exhibit high quantum yield of singlet oxygen generation (0.87 in DMF), and is highly efficient and stable to initiate mineralization of cholorophenols in water under visible light irradiation.