Reactivity of hydroperoxide bound to a mononuclear non-heme iron site

The first isolation and spectroscopic characterization of the mononuclear hydroperoxo-iron(III) complex [Fe(H(2)bppa)(OOH)](2+) (2) and the stoichiometric oxidation of substrates by the mononuclear iron-oxo intermediate generated by its decomposition have been described. The purple species 2 obtained from reaction of [Fe(H(2)bppa)(HCOO)](ClO(4))(2) with H(2)O(2) in acetone at -50 degrees C gave characteristic UV-vis (lambda(max) = 568 nm, epsilon = 1200 M(-1) cm(-1)), ESR (g = 7.54, 5.78, and 4.25, S = (5)/(2)), and ESI mass spectra (m/z 288.5 corresponding to the ion, [Fe(bppa)(OOH)](2+)), which revealed that 2 is a high-spin mononuclear iron(III) complex with a hydroperoxide in an end-on fashion. The resonance Raman spectrum of 2 in d(6)-acetone revealed two intense bands at 621 and 830 cm(-1), which shifted to 599 and 813 cm(-1), respectively, when reacted with (18)O-labeled H(2)O(2). Reactions of the isolated (bppa)Fe(III)-OOH (2) with various substrates (single turnover oxidations) exhibited that the iron-oxo intermediate generated by decomposition of 2 is a nucleophilic species formulated as [(H(2)bppa)Fe(III)-O*].     

Side chain type ionic liquid crystalline polymers having high Preliminary communication molecular weight

Side chain type ionic liquid crystalline polymers having a 4-(1,3-dioxan-2-yl)pyridinium structure in their mesogenic side chain were synthesized. These polymers exhibited the smectic A phase. The molecular weights of these ionic liquid crystalline polymers are very high, e.g. for compound 7 - 2 M _w = 486 000.     

Macroscopic energy diffusion for a chain of anharmonic oscillators

We study the energy diffusion in a chain of anharmonic oscillators where the Hamiltonian dynamics is perturbed by a local energy conserving noise. We prove that under diffusive rescaling of space–time, energy fluctuations diffuse and evolve following an infinite dimensional linear stochastic differential equation driven by the linearized heat equation. We also give variational expressions for the thermal diffusivity and some upper and lower bounds.     

Creation of Chiral Thixotropic Gels through a Crown–Ammonium Interaction and their Application to a Memory‐Erasing Recycle System

A unique class of oligothiophene‐based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one‐dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown–ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode.     

Monocyclic rod-type liquid crystals; 2,5-dialkanoyloxytropones and 5-alkanoyloxy-2-alkoxytropones

Two kinds of monocyclic troponoid mesogens, 2,5-dialkanoyloxytropones (4) and 5-alkanoyloxy2-alkoxytropones (5), were prepared. The former showed monotropic smectic A phases and the virtual isotropic liquid-smectic A transitions of the latter were determined by extrapolation of results in a binary phase diagram. Comparing the mesogenic properties between the tropones 4 and the 2-alkanoyloxy-5-alkoxytropones (1), the alkanoyloxy group at C-5 enhances both the melting points and the transition temperatures of the smectic A phases. From the comparison between 5 and 1, the alkanoyloxy group at C-2 lowers the melting points.     

Synthesis of nonplanar bipyridyls bridged by disilane and disiloxane and their phosphorescent copper complexes

Disilane- and disiloxane-bridged bipyridyls ( DSBPy and DSOBPy ) were prepared and their optical properties were investigated in comparison with those of previously reported monosilane- and monogermane-bridged counterparts. The UV–visible absorption and photoluminescence bands of DSBPy and DSOBPy were blue-shifted as a result of elongation of the bridging units from monosilane and monogermane to disilane and disiloxane, likely due to the enhanced twisting of the bipyridyl units. Phosphorescent complexes DSBPy–Cu and DSOBPy–Cu were prepared by the interaction of DSBPy and DSOBPy with Cu₂I₂(PPh₃)₂. X-ray diffraction studies of their single-crystal structures revealed polymeric structures composed of repeat units of DSBPy or DSOBPy and [Cu^II(PPh₃)]₂. Organic light-emitting diodes with the ITO/PEDOT:PSS/ DSBPy–Cu or DSOBPy–Cu :PCTSQ/TAZ/Al structure were fabricated to examine the applications of the complexes as electroluminescent materials. The devices emitted yellow light with emission maxima at approximately 600 nm, and maximal luminance reached 120 and 190 cd m⁻² for devices based on DSBPy–Cu and DSOBPy–Cu , respectively. The performance of the DSOBPy–Cu -based device was improved by using TAZ as the dopant of the emissive layer, and luminance was increased to 390 cd m⁻².     

Effects of silica nanoparticle addition on polymer semiconductor wettability and carrier mobility in solution‐processable organic transistors on hydrophobic substrates

The effects of the addition of silica nanoparticles (SNPs) on wettability of regioregular poly(3‐hexylthiophene) (P3HT) organic semiconductor solutions on hydrophobic substrates and the carrier mobility in organic field‐effect transistors (OFETs) made of these films are investigated. The dewetting of films made from P3HT solutions on hydrophobic substrates modified with octadecyltrichlorosilane (ODTS) is markedly suppressed after the addition of SNPs with phenyl surfactants. This enables us to fabricate continuous P3HT/SNPs films with high crystallinity by the conventional spin‐coating technique, leading to higher mobility compared with P3HT FETs fabricated on non‐modified substrates. Moreover, the addition of SNPs with larger diameters compensates for the degradation of mobility associated with the increase in the concentration of SNPs. Solution‐processed P3HT/SNPs FETs on ODTS‐modified substrates exhibit a field‐effect mobility of 1.3 × 10^?2 cm² V^?1 s^?1, which is almost comparable to that of P3HT FETs without SNPs (2.1 × 10^?2 cm² V^?1 s^?1). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 509–516     

Recent Developments in Asymmetric Phase‐Transfer Reactions

Phase‐transfer catalysis has been recognized as a powerful method for establishing practical protocols for organic synthesis, because it offers several advantages, such as operational simplicity, mild reaction conditions, suitability for large‐scale synthesis, and the environmentally benign nature of the reaction system. Since the pioneering studies on highly enantioselective alkylations promoted by chiral phase‐transfer catalysts, this research field has served as an attractive area for the pursuit of “green” sustainable chemistry. A wide variety of asymmetric transformations catalyzed by chiral onium salts and crown ethers have been developed for the synthesis of valuable organic compounds in the past several decades, especially in recent years.