Aryne reaction with trifluoromethyl ketones in three modes: C-C bond cleavage, [2+2] cycloaddition and O-arylation

Trifluoromethyl ketones were found to be coupled with arynes in three modes depending upon their substitution patterns, namely C-C bond cleavage, [2+2] cycloaddition and O-arylation.     

Functionalization of a simple dithienylethene via palladium-catalyzed regioselective direct arylation

The direct arylation on the thienyl groups of a diarylethene with various aryl iodides efficiently provided arylated dithienylethenes under palladium catalysis. Unsymmetrically substituted dithienylethenes were also synthesized by this protocol. This procedure allows a rapid access to a variety of aryl-substituted dithienylethenes from a single substrate of a simple dithienylethene.     

Curved Ferroelectric Liquid Crystal Matrix Displays Driven by Field-Sequential-Color and Active-Matrix Techniques

This paper describes a curved field-sequential-color matrix display using fast-response ferroelectric liquid crystal. Black matrix and transparent electrode patterns were formed on a thin plastic substrate by a transfer method from a glass substrate. While a composite film of liquid crystal and micro-polymers of walls and fibers was formed between the flexible substrates by printing, laminating and curing processes of a solution of monomers and liquid crystal, the mechanical stability was enhanced by use of multi-functional monomers to form large display panels. The image pixels of the matrix panel were driven by an active matrix scheme using an external switch transistor array at a frequency of 180 Hz for intermittent three-primary-color backlight illumination. The flexible A4-paper-sized color display with 24 × 16 pixels and 60 Hz field frequency was demonstrated by illuminating it with sequential three-primary-color lights from light-emitting diodes of the backlight. Our display system is useful in various information displays because of its freedom of setting and location.     

Regioselective Borylation of Porphyrins by C?H Bond Activation under Iridium Catalysis to Afford Useful Building Blocks for Porphyrin Assemblies

Highly regioselective and efficient borylation of a variety of porphyrins has been achieved by reaction with bis(pinacolato)diboron through C? H bond activation under iridium catalysis on the basis of the synthetic protocol developed by Miyaura, Hartwig, and Smith. A boryl group can be selectively introduced at sterically uncongested positions in the peripheral aryl groups of porphyrin substrates whose peripheral β‐positions are sterically hindered. Curiously, β substituents adjacent to the aryl group to be borylated have unexpectedly large effects on the regioselectivity, because the iridium catalyst can discriminate between subtle steric differences. Chemoselective borylation was also achieved for several functionalized porphyrins. This borylation protocol can be applied to various monomeric and oligomeric functional porphyrins, hence offering an efficient route to elaborate multiporphyrin‐based molecular constructs.     

Ab initio theoretical calculations of the electronic excitation energies of small water clusters

A direct ab initio molecular dynamics method has been applied to a water monomer and water clusters (H(2)O)(n) (n = 1-3) to elucidate the effects of zero-point energy (ZPE) vibration on the absorption spectra of water clusters. Static ab initio calculations without ZPE showed that the first electronic transitions of (H(2)O)(n), (1)B(1)←(1)A(1), are blue-shifted as a function of cluster size (n): 7.38 eV (n = 1), 7.58 eV (n = 2) and 8.01 eV (n = 3). The inclusion of the ZPE vibration strongly affects the excitation energies of a water dimer, and a long red-tail appears in the range of 6.42-6.90 eV due to the structural flexibility of a water dimer. The ultraviolet photodissociation of water clusters and water ice surfaces is relevant to these results.     

The direct molecular orbital dynamics study on the hydrogen species adsorbed on the surface of planar graphite cluster model

In order to investigate thermal behaviors of the hydrogen species, H⁺ ion and H atom, adsorbed on the surface of planar graphite, the direct molecular orbital dynamics (MO) calculations at AM1 level are applied to the hydrogen terminated planar cluster models included by the species, C₅₄H₁₈·H⁺ and C₅₄H₁₈·H, respectively. This is the first trial to describe the thermal behaviors of these species in terms of MO dynamics. Both hydrogen species form the covalent bonds with the surface carbon atoms through the sp³ hybrid orbitals which inhibit their dissociation at high temperature up to 2000 K. It was found that the reduction of band gap is introduced by the adsorption of H⁺ ion.     

Phenylselenenyl chloride in acetonitrile-water : A highly convenient reagent for hydroxyselenation of olefins and preparation of cyclic ethers from dienes

The reaction of phenylselenenyl chloride with olefins in aqueous acetonitrile affords β-hydroxyalkyl phenyl selenides in excellent yields, providing the most convenient method for hydroxyselenation of olefins so far reported. When the reaction was applied to conjugated dienes, monohydroxyselenated products were obtained in good to excellent yields. From non-conjugated dienes, on the other hand, cyclic ethers containing two phenylseleno groups were produced in good to excellent yields, the first step of this reaction being the hydroxyselenation of one double bond.