Preparation and properties of solvent-soluble bridged polybiphenylenes and related copolymers

A solvent-soluble polybiphenylene with a single hetero atom in the chain (a bridged polybiphenylene) was prepared according to the synthetic procedure for a solvent-soluble poly(4,4′-biphenylene). In addition, a related copolymer was similarly prepared by the addition of the MMA monomer in the reaction system. The thermal properties and viscosity behavior of each product were influenced by the hetero atom, especially by the introduction of MMA component in the chain. Each viscosity curve (η_sp/c vs. c) shows an anomalous peak at a specific concentration (0.3–0.002 g/100 ml DMF), depending upon the atomic group. The η_sp/c value for each homopolymer was not over 0.1 except in the neighborhood of the anomalous peak, while those for copolymers became 3–4 times larger than values for corresponding homopolymers. It is obvious that the viscosity of each copolymer increases due to an increase in flexibility due to introduction of the MMA units in the chain, since little difference in molecular weights is found between homopolymers (16,000–15,000) and copolymers (10,000–12,000).     

Electrophilic Cyanation of Boron Enolates: Efficient Access to Various β‐Ketonitrile Derivatives

The highly efficient electrophilic cyanation of boron enolates using readily available cyanating reagents, N‐cyano‐N‐phenyl‐p‐toluenesulfonamide (NCTS) and p‐toluenesulfonyl cyanide (TsCN), is reported. Various β‐ketonitriles were prepared by this new protocol, which has a remarkably broad substrate scope compared to existing methods. The present method also allowed efficient synthesis of β‐ketonitriles containing a quaternary α‐carbon center. In addition, a preliminary result with the use of a chiral boron enolate for the enantioselective cyanation reaction is described.     

Interphase Transfer of Tackifier between Immiscible Rubbers

Interphase transfer of a coumarone-indene tackifier between natural rubber (NR) and poly(isobutylene) (PIB) was studied. The laminated sheets, composed of a sheet of NR with the tackifier and a sheet of PIB with the tackifier, were annealed at various temperatures to promote the interphase transfer of the tackifier. After separating the two sheets, the infrared spectra were measured to evaluate the tackifier content in each rubber sheet. It was found that a large amount of the tackifier resided in PIB after annealing at ?20°C, whereas the tackifier moved to NR at 40°C. Consequently, the NR sheet exhibited a lower glass transition temperature T_g after annealing at ?20°C and a higher T_g when annealed at 40°C. The differential scanning calorimetry measurements revealed that the crystallization of NR was responsible for the tackifier transfer. This phenomenon should be of interest because the tackifier transfer, which results in the T_g shift of each rubber, would also occur in a blend system. When NR is the matrix of the blend, it would be an ideal blend because the matrix would show a low T_g in winter and a high T_g in summer.     

Theoretical studies on the photochemical reaction mechanisms of o-xylylene. Effects of phenyl group for electrocyclic reaction mechanism

The potential energy surfaces (PESs) of the electrocyclic reactions of o-xylylene at the ground and the lowest excited states are calculated by CASSCF molecular orbital and MRMP2 methods. The lowest excited state geometry of o-xylylene has C(2v) symmetry and is about 65 kcal mol(-1) in energy above the ground state. The PESs in the vicinity of the conical intersection are different from those of the electrocyclic reaction of cis-butadiene. In the vicinity of the conical intersection, the transition state at the ground state relating to methylene-cycloheptadienyl carbene is located. The transition state is only 4.3 kcal mol(-1) lower in energy than the conical intersection at the CASSCF(10,10)/6-31G(d) level and 0.5 kcal mol(-1) lower at the MRMP2/6-311+G(d,p) level. The transition state corresponding to benzocyclobutene does not locate in the vicinity of the conical intersection because of the resonance energy between benzene ring and methylene group.     

Orientational ordering of crystal domains in ionic liquid based mixtures

By in situ observations using simultaneous X-ray diffraction and the DSC (differential scanning calorimetry) method, the effect of water, methanol, ethanol, and benzene on the crystallization has been observed in an ionic liquid (IL)-rich phase. The IL is a hydrophilic ionic liquid, N, N-diethyl-N-methyl-N-2-methoxyethyl ammonium tetrafluoroborate, [DEME][BF4]. At a small amount of the above additional molecules in the IL, the conventional preferred orientation on the Debye rings was seen by the X-ray diffraction. At 0.9 mol % H2O, twinlike crystal domains develop extraordinary on the microdomains. By the "crystal-growth enhancement effect" at a slight amount of water, a composite domain structure, which consists of the large domain and the weakly orientated microdomains, is formed without internal strains. Above 2.9 mol % H2O, the domain structure, however, disappears completely. It is remarkable that, in a thermal cycling experiment using pure [DEME][BF4], the similar composite domain structure appeared. This is also caused by an uptake of a slight amount of water.     

Reduced stress‐optical coefficient of polycarbonate by antiplasticization

We have investigated the effect of antiplasticization on the stress‐optical behavior of polycarbonate (PC) containing terphenyls (tPh) and di(2‐ethylhexyl)adipate (DEHA). Addition of the three tPhs (p‐, o‐, and m‐tPh) and DEHA at contents of 5–10 wt % increases the tensile storage modulus (E' ) of PC owing to the antiplasticization effect. In particular, p‐tPh increases E' more than the other additives, suggesting that the rod‐like shape matches the free volume of PC in the glassy state. The three tPh isomers improve the glassy birefringence of PC while DEHA does not change the glassy birefringence, which corresponds to the polarizability anisotropy. The stress‐optical coefficient, a ratio of stress and birefringence, of PC decreases with increasing additive content in order of p‐tPh ? o‐tPh > m‐tPh = DEHA. This result is agreement with a restricted rotational motion of additive molecule in PC, which is observed in dynamic mechanical and birefringence data. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1837–1842     

Magnetic Correlation Engineering in Spin-Sandwiched Layered Magnetic Frameworks

The insertion of “sandwiched spins” between magnetic layers could efficiently affect the interlayer magnetic correlations, but doing so increases the complexity in the interlayer spin alignment because of competition between the inserted spin-layer interaction J_NNI and the interlayer through-space interaction J_NNNI if the magnitude of J_NNI is of the same order as J_NNNI with reciprocal signs of the respective interactions. Herein, systematic tuning of the magnetic phase variations by J_NNI and J_NNNI in two kinds of metal-variable isostructural series of supramolecular pillared layer magnets [MCp*₂][{Ru₂^II,II(2,3,5,6-F₄CO₂)₄}₂(TCNQ)] ⋅ 2 DCE (M=Co, Fe, Cr; 2,3,5,6-F₄PhCO₂⁻=2,3,5,6-tetrafluorobenzoate; TCNQ=7,7,8,8-tetracyano-p-quinodimethane; DCE=1,2-dichloroethane) and their DCE-free series, in which [MCp*₂]⁺ (Cp*=η⁵-C₅Me₅) species with S=0, 1/2, and 3/2 for M=Co, Fe, Cr, respectively, are sandwiched between ferrimagnetic layers of [{Ru₂}₂(TCNQ)]⁻, is demonstrated. The results showed that the flexible magnetic natures of these magnets are changeable in dependence on J_NNI and J_NNNI, as well as on interlayer inserted spins M.     

Regulating Higher‐Order Organization through the Synergy of Two Self‐Sorted Assemblies

The extracellular matrix (ECM) is the natural fibrous scaffold that regulates cell behavior in a hierarchical manner. By mimicking the dynamic and reciprocal interactions between ECM and cells, higher‐order molecular self‐assembly (SA), mediated through the dynamic growth of scaffold‐like nanostructures assembled by different molecular components, was developed. Designed and synthesized were two self‐sorted coumarin‐based gelators, a peptide molecule and a benzoate molecule, which self‐assemble into nanofibers and nanobelts, respectively, with different dynamic profiles. Upon the dynamic growth of the fibrous scaffold assembled from peptide gelators, nanobelts assembled from benzoate gelators transform into a layer‐by‐layer nanosheet, reaching ninefold increase in height. By using light and an enzyme, the spatial–temporal growth of the scaffold can be modified, leading to in situ height regulation of the higher‐order architecture.