Catalytic Alkynylation of Polyfluoroarenes by Amide Base Generated In Situ

We herein demonstrate that the amide base generated in situ from CsF and N(TMS)₃ catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds.     

Molecular Insights into the Ligand-Based Six-Proton- and Six-Electron-Transfer Processes Between Tris-ortho-Phenylenediamines and Tris-ortho-Benzoquinodiimines

The global demand for energy and the concerns over climate issues renders the development of alternative renewable energy sources such as hydrogen (H₂) important. A high-spin (hs) Fe^II complex with o-phenylenediamine (opda) ligands, [Fe^II(opda)₃]²⁺ (hs- [6R] ²⁺), was reported showing photochemical H₂ evolution. In addition, a low-spin (ls) [Fe^II(bqdi)₃]²⁺ (bqdi: o-benzoquinodiimine) (ls- [0R] ²⁺) formation by O₂ oxidation of hs- [6R] ²⁺, accompanied by ligand-based six-proton and six-electron transfer, revealed the potential of the complex with redox-active ligands as a novel multiple-proton and -electron storage material, albeit that the mechanism has not yet been understood. This paper reports that the oxidized ls- [0R] [PF₆]₂ can be reduced by hydrazine giving ls-[Fe^II(opda)(bqdi)₂][PF₆]₂ (ls- [2R] [PF₆]₂) and ls-[Fe^II(opda)₂(bqdi)][PF₆]₂ (ls- [4R] [PF₆]₂) with localized ligand-based proton-coupled mixed-valence (LPMV) states. The first isolation and characterization of the key intermediates with LPMV states offer unprecedented molecular insights into the design of photoresponsive molecule-based hydrogen-storage materials.     

Hydrogen-induced magnetic and structural transformations of GdCu

The magnetization of GdCu induced by hydrogen uptake was measured within the temperature range of 4.2 to 300 K, occurring phase changes were followed by X-ray diffraction measurements at ambient temperature. The prepared GdCu powder of CsCl-type structure readily absorbed hydrogen at ambient temperature, where hydrogen pressure was below 100 kPa. Hydrogenation changed the magnetism of GdCu in a complex manner from an antiferromagnetic-like type to a paramagnetic-like one. The changes in magnetic properties of GdCu by hydrogenation are governed by hydrogen-induced disproportionation. Within the composition range 0<[H]/[GdCu]<1, GdCu disproportionated according to 2GdCu+H₂→GdH₂+GdCu₂ . The magnetization was evaluated by the expression χ_total=(1-x)χ_GdCu+(x/2)(χ_GdH2+χ_GdCu2). GdCu hydride was not observed. Hydrogenation beyond [H]/[GdCu]>1 gave rise to the disproportionation of GdCu₂ causing the change in magnetization.     

Hausdorff measures and packing measures of limit sets of CIFSs of generalized complex continued fractions

ABSTRACT

We consider a certain family of CIFSs of the generalized complex continued fractions with a complex parameter space. We show that for each CIFS of the family, the Hausdorff measure of the limit set of the CIFS with respect to the Hausdorff dimension is zero and the packing measure of the limit set of the CIFS with respect to the Hausdorff dimension is positive (main result). This is a new phenomenon of infinite CIFSs which cannot hold in finite CIFSs. We prove the main result by showing some estimates for the unique conformal measure of each CIFS of the family and by using some geometric observations.     

Structural and superconductivity study on α-FeSex

We have successfully synthesized the α-FeSe_x binary tetragonal superconductors with nominal composition of FeSe_x (x=0.6-1.0) via conventional solid state reactions between Fe and Se sealed in quartz tubes. Fe and β-FeSe are the most commonly seen impurities in this binary system. A low-temperature annealing at 400 °C is found to be crucial to remove β-FeSe, which is the thermodynamic stable phase with hexagonal symmetry. For all the samples of FeSe_x, superconductivity is confirmed by magnetic measurements as well as resistivity measurements with their T_c at around 8 K. We noticed that their T_c does not vary with the different nominal Se amount. High-resolution synchrotron X-ray diffraction analysis revealed that the unit cell parameters of all these samples do not change within the error range, and their structure only tolerate the same very small amount of Se deficiency. Based on this study, we concluded that the α-FeSe_x superconductor only exist in a very narrow deficiency range.     

The mineralization of CO32− ions on chitin- or chitosan- metal composite beads in water

The following dry composite beads (diameter 1.0-1-2 mm) were prepared: chitin-CaCO₃, chitosan-CaCl₂. chitosan-CuCl₂, partially N-acetylated chitosan-CuCl₂, chitosan-CuSO₄, chitosan-Fe₃O₄, chitin-SiO₂. Each of chitosan-CuCl₂, chitosan-CuSO₄ and chitin-CaCl₂ composite beads was treated in aqueous K₂CO₃ at room temperature to afford a mixture of metal carbonates and hydroxides on chitin or chitosan chain.     

Facile synthesis of enantiopure 1,1′-binaphthyl-2,2′-dicarboxylic acid via lipase-catalyzed kinetic resolution

Enantiopure 1,1′-binaphthyl-2,2′-dicarboxylic acids (R)-1 and (S)-1 have been synthesized through the lipase-catalyzed kinetic resolution of the racemic 2,2-bis(hydroxymethyl)-1,1′-binaphthyl (±)-2 and subsequent oxidation of the hydroxymethyl groups.     

Alkyl-functionalized organic dyes for efficient molecular photovoltaics

We designed and synthesized new alkyl-functionalized organic dyes, MK-1 and MK-2, for dye-sensitized solar cells (DSSCs). Based on the MK-2 dye, a high performance of efficiency (eta, 7.7%; short-circuit current density Jsc = 14.0 mA cm-2, open-circuit voltage Voc = 0.74 V, and fill factor FF = 0.74) was achieved under AM 1.5 G irradiation (100 mW cm-2). Remarkably, the relatively higher Voc for DSSCs based on MK-1 and MK-2 dyes, which have long alkyl chains, were observed among the organic dyes caused by the increasing of the electron lifetime in the conduction band of TiO2. Our molecular design of alkyl-functionalized dyes strongly suggests the promising performance of molecular photovoltaics based on organic dyes.