Controllable Electronic Structures and Photoinduced Processes of Bay‐Linked Perylenediimide Dimers and a Ferrocene‐Linked Triad

A series of perylene‐3,4,9,10‐bis(dicarboximide) (PDI) dimers linked through the bay regions was systematically synthesized to examine the electronic structures and photophysical properties in dependence on the distance and orientation between the two PDI units. The spectroscopic and electrochemical measurements suggested that the coupling value of a directly linked PDI dimer (PDI)₂ is much larger than those of para‐ and meta‐phenylene‐bridged PDI dimers p‐(PDI)₂ and m‐(PDI)₂. The width of Davydov splitting was quantitatively evaluated to compare the coupling values between the two PDI units in these dimers by absorption spectroscopy in frozen 2‐methyl‐THF. Excimer formation of PDI dimers induced the strong fluorescence quenching and large red‐shifts. Femtosecond transient absorption revealed a broad absorption derived from an excimer in the range from about 600 nm to the near‐IR region. The rate constants of formation and decay of the excimer are strongly dependent on the coupling values. Time‐resolved measurements on ferrocene‐linked p‐(PDI)₂ revealed a competition between the photoinduced processes of electron transfer and excimer formation in PhCN, which is in sharp contrast with the sole electron‐transfer process in toluene.     

Ion chromatographic system with a novel switching suppression device

Ion chromatography (IC) has been a powerful tool for measuring ionic species in environmental samples such as tap, river and drain waters. Suppressor modules (membrane and disposable column types) have been used for reducing the background of a baseline. A new type of suppressor device, which has a suppressor resin and switching valve was developed. Fresh ionic resin is introduced into a groove for each analysis to perform the suppression of the working eluent. The eluent composition for obtaining higher sensitivity and better resolutions among ionic species and carbonate ion was also investigated. Although carbonate buffers are used for ion separation in general, the separation of carbonate ion from other ions was not achieved. A borate eluent resulted in good resolutions and higher sensitivity. A new column was also developed for obtaining higher column efficiency and resolution. The optimization of anion separation using a new IC system (IC-2001) that consists of a new suppressor device, an anion-exchange column (TSKgel SuperIC-Anion, 150x4.6 mm), an autosampler, a conductivity cell and a pump in a compact module is described.     

Piled-lamellae structure in polyethylene film and its deformation

The fine structure of polyethylene film has been investigated by using a high-resolution scanning electron microscope equipped with a field emission source. The original film surface of a-axis-oriented blown polyethylene film and the surface of a necked region formed by drawing the film in the machine direction were observed. High magnification electron micrographs indicate that the basic unit of internal texture of this film consists of piled-lamellae units, each pile containing three to ten lamellar crystal sheets. The piled-lamellae unit acts as one body and does not separate into single lamellae during deformation. Many tie fibrils are formed between adjacent piled-lamellae units, when the film is drawn in the machine direction. Although little attention has been given to this mechanism, it is important in deformation. This fact seems to be reflected in different shapes of the stress-strain curves of films drawn the machine direction and perpendicular to it.     

Infrared spectroscopic studies of polymer transitions. III. Effects of sodium ion on glass transitions in styrene-based ionomers

The glass transition in styrene-based ionomers was investigated by means of infrared spectroscopy and differential scanning calorimetry (DSC). Transition temperatures were determined from the temperature dependence of the peak absorbances of the 1700 and 1745 cm^?1 bands. These transition temperatures agreed with glass transition temperatures (T_g) determined by DSC. With increasing degree of ionization, T_g and the enthalpy ΔH of the residual intermolecular hydrogen bonding increased. The values of T_g obtained were analyzed by the theory of Fox and Loshaek for the effect of crosslinks. It is concluded that sodium ions probably from ionic domains and act as crosslinks to reinforce the residual hydrogen bonding and may increase T_g. The absorbance at 1560 cm^?1 (ν_COO^?) did not change at T_g. This suggests that the glass transition observed here is not due to the onset of the mobility in ionic domains, as has been proposed for ethylene-based ionomers on the basis of dielectric measurements.     

Preparation of soluble and fusible poly(2,5-dimethoxy-1,4-phenylene)

Poly(2,5-dimethoxy-1,4-phenylene) was prepared by oxidative polymerization of p-dimethoxybenzene with aluminum chloride and copper(II) chloride in nitrobenzene under reduced pressure. The polymers obtained were soluble in sulfuric acid and fusible at 320°C. The intrinsic viscosity of the polymer was ca. 0.07 in sulfuric acid. Demethylation of methoxy groups did not occur during the polymerization.     

On the Absence of Non-Periodic Ground States for the Antiferromagnetic XXZ Model

We prove that the antiferromagnetic XXZ model with Ising-like anisotropy on a one-dimensional lattice does not have non-periodic ground states.     

Possible one-dimensional 3He quantum fluid formed in nanopores

Heat capacity measurements have been made down to 5 mK for 3He fluid films adsorbed in one-dimensional (1D) nanometer-scale pores, 28 A in diameter, preplated with 4He of 1.47 atomic layers. At low 3He density, the heat capacity shows a density-dependent, Schottky-like peak near 150 mK asymptoting to the value corresponding to a 2D Boltzmann gas at high temperatures. The peak behavior is attributed to the crossover from a 2D gas to a 1D state at low temperatures. The degenerate state of the 1D 3He fluid is indicated by a predominantly linear temperature dependence below about 30 mK.     

Localization-dependent photoluminescence spectrum of biexcitons in semiconductor quantum wires

We study exciton and biexciton spectra in disordered semiconductor quantum wires by means of nanophotoluminescence spectroscopy. We demonstrate a close link between the exciton localization length along the wire and the occurrence of a biexciton spectral line. The biexciton signature appears only if the corresponding exciton state extends over more than a few tens of nanometers. We also measure a nonmonotonous variation of the biexciton binding energy with decreasing exciton localization length. This behavior is quantitatively well reproduced by the solution of the single-band Schr?dinger equation of the four-particle problem in a one-dimensional confining potential.     

Crystalline inclusion compounds constructed through self-assembly of isonicotinic acid and thiocyanato coordination bridges

The synthesis, crystal structures, inclusion ability, and structural robustness of novel crystalline inclusion compounds of [Ni(SCN)2(isoH)2].xG (isoH = isonicotinic acid; G = aromatic guest) are described. The inclusion compounds are constructed by stacking identical 2D host layers that consist of SCN-, isoH, and Ni2+ with van der Waals contact separation. In the layer, two types of rectangular cavities (A-type and B-type) are formed, and the guests are included in the former cavity. The inclusion compounds were categorized into four stacking modes according to the difference in the stacking mode of the layers. A systematic investigation of the crystal structures of the 21 inclusion compounds clarified the close relationship between the molecular structure of the guest and the resultant stacking mode of the layers.