Thin films of peroxopolytungstic acids: applications to optical waveguide components

Thin films of peroxohetero(carbon)polytungstic acid (CW-HPA) and carbon-free isopolytungstic acid (W-IPA) were prepared, and examined in terms of optical and etching properties. Thermal decomposition was found to give good results in removing excess hydrogen peroxide (H₂O₂) during the preparation of CW-HPA and W-IPA. It was shown for the first time that thin films of CW-HPA and W-IPA have very high refractive indices (larger than 2.0) when sufficiently dried. Optical waveguide (OWG) characteristics of these films were examined using a slab-type OWG structure and ARROW (Antiresonance Reflection Optical Waveguide)-type structures. An embossing technique was applied to make diffractional grating couplers.     

The exchange interaction in the radical pair in 2-propanol solution as studied by the CIDNP multiplet pattern

The exchange interaction in the radical pair in homogeneous solution has been investigated by using the CIDNP method. The experimental observations of the multiplet pattern were compared with the theoretical simulations in which the exchange integral was a variable parameter. The results show that 2-propanol is a unique solvent in that the exchange integral in the radical pair in this solvent is large.     

Formal Synthesis of Sarain A: Intramolecular Cycloaddition of an Eight‐Membered Cyclic Nitrone to Construct the 2‐Azabicyclo[3.3.1]nonane Framework

An enantioselective route to the tetracyclic skeleton of sarain A has been developed. Asymmetric reduction of an ynone introduced a chiral center which was transferred to the contiguous tertiary stereogenic centers through an Ireland–Claisen rearrangement. The 2‐azabicyclo[3.3.1]nonane framework was constructed by an unprecedented intramolecular cycloaddition of an eight‐membered cyclic nitrone. Using the steric bias of the bicyclic system, the quaternary carbon atom was constructed by a stereoselective aldol reaction. Further ring formations were performed by ring‐closing metathesis for the 13‐membered ring and an iodoamidation reaction for the pyrrolidine ring. The present synthesis has successfully provided an alternative route to the late‐stage intermediate of Overman’s synthesis.     

Efficient Synthesis,Structure, and Complexation Studies of Electron‐Donating Thiacalix[n]dithienothiophene

A series of thiacalix[n]dithiothiophenes (n=4–10) was prepared by a facile method and X‐ray analysis was used to determine the molecular structures of square‐ (4‐mer) and pentagonal‐shaped macrocycles (5‐mer). In the cyclic voltammograms, reversible multielectron redox processes, which are due to electronic delocalization, were observed at low oxidation potentials. The cyclic 4‐mer acted as a “Janus‐head” cavitand for two C₆₀ molecules, whereas the 5‐ and 6‐mer formed stable 1:1 complexes with C₆₀ .     

Comparative study on the photocatalytic properties of Ag3PO4 fabricated by different methods

Research on Chemical Intermediates - A comparative study was carried out on the photocatalytic properties depending on Jodifferent morphologies of Ag3PO4 fabricated by different methods, i.e. as...     

Oxo-tethered ruthenium(II) complex as a bifunctional catalyst for asymmetric transfer hydrogenation and H2 hydrogenation

Newly developed oxo-tethered Ru amido complexes (R,R)-1 and their HCl adducts (R,R)-2 exhibited excellent catalytic performance for both asymmetric transfer hydrogenation and the hydrogenation of ketonic substrates under neutral conditions without any cocatalysts to give chiral secondary alcohols with high levels of enantioselectivity.     

Phase behavior of binary mixtures composed of ethylene carbonate and various organic solvents

Phase behaviors of the binary mixtures composed of ethylene carbonate (EC) and aliphatic alcohols, ω-phenyl alcohols, and alkylbenzenes were investigated. In addition, heat of solution of EC into these organic solvents was measured. The EC/methanol and EC/ethanol systems gave homogeneous solution at the temperature above their liquidus lines, while the mixtures of EC and alcohols with longer alkyl chain showed a miscibility gap in a liquid phase and provided the monotectic-type phase diagram. The liquid–liquid phase separation region expanded with the increase in the alkyl chain length. A similar phase behavior was also observed for the mixtures of EC and alkylbenzenes. On the other hand, the EC mixtures with ω-phenyl alcohols showed no miscibility gap in a liquid phase at least up to 4-phenylbutan-1-ol which has C4 alkyl chain intervening between phenyl and hydroxyl groups. This result demonstrates that both of the hydroxyl and phenyl groups act to facilitate the mixing of aliphatic compounds with EC. The phase behavior of these EC mixtures was analyzed applying the modified regular solution model in which the pair interaction energy was regarded as free energy. The model calculation with the use of heat of solution of EC at infinite dilution as the pair interaction enthalpy reproduced well both of the experimentally obtained liquidus line and mutual solubility curve as well as monotectic point.     

Star-shaped pyrrole-fused tetrathiafulvalene oligomers: synthesis and redox, self-assembling, and conductive properties

A series of star-shaped pyrrole-fused tetrathiafulvalene (TTF) oligomers 1-3 was synthesized via an S(N)Ar reaction of fluorinated benzenes with the pyrrolyl sodium salts. Electrochemical and chemical oxidations of 1-3 revealed that a radical cation moiety on each TTF unit was successfully accumulated in all oligomers. Self-assembled structures of neutral and oxidized species were characterized by SEM and XRD, and their conductive properties of the iodine-doped 1-3 as well as an intermolecular mixed-valence ion radical salt were investigated.