A convenient synthesis of 2-substituted indoles by the reaction of 2-(chloromethyl)phenyl isocyanides with organolithiums

The reaction of 2-(chloromethyl)phenyl isocyanides, readily available by dehydration of the respective N-[2-(chloromethyl)phenyl]formamides, with organolithiums produced 2-substituted indoles in satisfactory yields through addition of organolithiums to the isocyano carbon followed by intramolecular substitution reaction of the resulting imidoyl anion intermediates.     

Polymerization and copolymerization of functionalized 2‐alkoxy‐1‐methylenecyclopropanes to form new polymers having alkoxy substituents

The polymers with functionalized alkoxy groups and with narrow molecular weight distribution (M_w/M_n < 1.12) are obtained from the living polymerization of 2‐alkoxy‐1‐methylenecyclopropanes using π‐allylpalladium complex, [(PhC₃H₄)Pd(μ‐Cl)]₂, as the initiator. The polymers with oligoethylene glycol groups in the alkoxy substituent are soluble in water, and hydroboration of the C?C double bond and ensuing addition of the OH groups to C?N bond of alkyl isocyanate produce the polymers with urethane pendant groups. The reaction decreases solubility of the polymer in water significantly. Di‐ and triblock copolymers of the 2‐alkoxy‐1‐methylenecyclopropanes are prepared by consecutive addition of the two or three 2‐alkoxy‐1‐methylenecyclopropane monomers to the Pd initiator. The polymers which contain both hydrophobic butoxy or tert‐butoxy group and hydrophilic oligoethylene glycol group dissolve in water and/or organic solvents, depending on the substituents. The ¹H NMR spectrum of poly( 1a ‐b‐ 1h ) (? (CH₂C(?CH₂)CHOBu)_n? (CH₂C(?CH₂)CH(OCH₂CH₂)₃OMe)_m? ) in D₂O solution exhibits peaks because of the butoxy and ?CH₂ hydrogen in decreased intensity, indicating that the polymer forms micelle particles containing the hydrophilic segments in their external parts. Aqueous solution of the polymer with a small amount of DPH (DPH = 1,6‐diphenyl‐1,3,5‐hexatriene) shows the absorbance due to DPH at concentration of the polymer higher than 5.82 × 10^?5 g mL^?1. Other block copolymers such as poly( 1b ‐b‐ 1h ) and poly( 1a ‐b‐ 1g ) also form the micelles that contain DPH in their core. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 959–972, 2009     

Is Auger-free luminescence present in CeF3?

It is well known that Auger-free luminescence (AFL) is observable when the condition E_g>E_VC is satisfied, where E_g is the band-gap energy between the lowest unoccupied band and the highest occupied band and E_VC the energy difference between the top of the highest occupied band and the top of the next lower occupied band. From measurements of reflection and X-ray photoelectron spectra, CeF₃ is demonstrated to really satisfy this condition. No evidence for AFL is found, nevertheless. The absence of AFL in CeF₃ is related to a characteristic nature of its highest and next lower occupied bands, which are quite different from those of previously studied AFL-materials.     

Lattice-driven cellular automata implementing local semantics

We propose a model based on Elementary Cellular Automata (ECA) where each cell has its own semantics defined by a lattice. Semantics play the following two roles: (1) a state space for computation and (2) a mediator generating and negotiating the discrepancy between the rule and the state. We call semantics playing such roles ‘local semantics’. A lattice is a mathematical structure with certain limits. Weakening the limits reveals local semantics. Firstly, we implement local semantics for ECA and call the result ‘Lattice-Driven Cellular Automata’ (LDCA). In ECA rules are common and invariant for all cells, and uniquely determine the state changes, whereas in LDCA rules and states interplay with each other dynamically and directly in each cell. Secondly, we compare the space-time patterns of LDCA with those of ECA with respect to the relationship between the mean value and variance of the ‘input-entropy’. The comparison reveals that LDCA generate complex patterns more universally than ECA. Lastly, we discuss the observation that the direct interplay between levels yields wholeness dynamically.     

Alternating π‐conjugated copolymer of dithiafulvene with 2,2′‐bipyridyl units

A π‐conjugated polymer containing a dithiafulvene unit and a bipyridyl unit was prepared by cycloaddition polymerization of aldothioketene derived from 5,5′‐diethynyl‐2,2′‐bipyridine. Ultraviolet–visible (UV–vis) absorption spectra showed that the π‐conjugation system of the polymer expanded more effectively than that of a benzene analogue of poly(dithiafulvene) obtained from 1,4‐diethynylbenzene. Cyclic voltammetry measurements indicated that the dithiafulvene–bipyridyl polymer was a weaker electron‐donor polymer than the benzene analogue. These results supported the idea that the incorporation of the electron‐accepting bipyridyl moiety into conjugated poly(dithiafulvene) induced an intramolecular charge‐transfer (CT) effect between the units. Treatment of the dithiafulvene–bipyridyl polymer with bis(2,2′‐bipyridyl)dichlororuthenium (II) [Ru(bpy)₂Cl₂] afforded a ruthenium–polymer complex. A cyclic voltammogram of the complex showed broad redox peaks, which indicated electronic interaction between the dithiafulvene and tris(bipyridyl) ruthenium complex. The dithiafulvene–bipyridyl polymer formed CT complexes with 7,7,8,8‐tetracycanoquinodimethane (TCNQ) in dimethyl sulfoxide. The UV–vis absorption indicated that the resulting CT complex contained anion radical of TCNQ and partially charge‐transferred TCNQ. The polymer showed an unusually high electrical conductivity of 3.1 × 10^?4 S/cm in its nondoped state due to the effective donor–acceptor interaction between the bipyridine unit and the dithiafulvene unit. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4083–4090, 2001     

Magnetic Alignment of Rhodamine B Intercalated in Synthetic Mica

Rhodamine B was intercalated in interlayer spaces of Somasif Me-100, a synthetic mica, and the obtained rhodamine B/Somasif hybrid was suspended in a UV-curable resin precursor. Then, the suspension was subjected to an applied rotating magnetic field to align the hybrid particles, followed by solidification of the medium by UV irradiation to fix the alignment. The hybrid particles were aligned so that the Somasif layer lay perpendicular to the axis of rotation of the applied rotating magnetic field. UV/vis measurement indicated that the transition moment of xanthene ring of rhodamine B lay inclined to the layer of Somasif.     

Syntheses and Properties of (Nitronyl nitroxide)-substituted Tri-phenylamine ortho-Bridged by Two Oxygen and Sulfur Atoms

A nitronyl nitroxide unit ( NN ) was linked with a triphenylamine-based condensed polycyclic skeleton DOTT to form a radical substituted donor NN - DOTT . X-ray crystal structure analysis demonstrated a flat bowl shape of the DOTT unit. EPR spectra showed the localization of electron spin on the NN unit. Chemical oxidation of the DOTT unit produced radical-substituted radical cation salts NN - DOTT ⁺ ⋅ SbF₆⁻ and NN - DOTT ⁺ ⋅ FeBr₄⁻ that are stable under ambient conditions. The magnetic behavior of NN - DOTT ⁺ ⋅ SbF₆⁻ is characterized by the strong intramolecular ferromagnetic interaction between NN and DOTT ⁺. The X-ray structural analysis of NN - DOTT ⁺ ⋅ FeBr₄⁻ shows planar structure of DOTT and 1D mixed-stack column of NN-DOTT ⁺ and FeBr₄⁻. Magnetic measurements established that NN - DOTT ⁺ ⋅ FeBr₄⁻ undergoes magnetic phase transition into a weak ferromagnet at 7 K.     

Synthesis of optically active bihelicenols

All six stereoisomers of dimethyl 5,5′-dihydroxy-1,1′,12,12′-tetramethyl-[6,6′]bi(benzo[c]phenanthrenyl)-8,8′-dicarboxylate (bihelicenol) were synthesized by the oxidative coupling of methyl 8-hydroxy-1,12-dimethylbenzo[c]phenanthrene-5-carboxylate (helicenol), and their structures were determined by X-ray analysis.