Desorption behavior of carrier free tritium from the inner surface of a glass ampoule

The desorption behavior of tritium from the glass ampoule which originally contained 37 GBq of carrier free tritium gas was studied by etching the surface with a diluted hydrofluoric acid solution or by heating at the constant rate up to 800 degrees C. The total amount of tritium sorbed on the inner surface of the ampoule was found to be 3.9 +/- 0.7 GBq. This value corresponded to more than 10% of tritium contained in the ampoule. The release rate of tritiated water (HTO) was 2.3 kBq/cm2.min, and the amount of HTO desorbed was strongly depended on the atmosphere. Thus, special precaution should be paid to the processing of a vessel once containing such an amount of tritium.     

Toward Ultralow-Bandgap Liquid Crystalline Semiconductors: Use of Triply Fused Metalloporphyrin Trimer-Pentamer as Extra-large π-Extended Mesogenic Motifs

In contrast with their dimeric homologue, triply fused zinc porphyrin trimer-pentamer, as extra-large π-extended mesogens, assemble into columnar liquid crystals (LCs) when combined with 3,4,5-tri(dodecyloxy)phenyl side groups (3?P(Zn) -5?P(Zn) , Figure?1). Their LC mesophases develop over a wide temperature range, namely, 41-280?°C (on heating) for 5?P(Zn) , and all adopt an oblique columnar geometry, typically seen in columnar LC materials involving strong mesogenic interactions. These LC materials are characterized by their wide light-absorption windows from the entire visible region up to a near infrared (NIR) region. Such ultralow-bandgap LC materials are chemically stable and serve as hole transporters, in which 5?P(Zn) gives the largest charge carrier mobility (2.4×10(-2) cm?V(-1) s(-1) ) among the series. Despite a big dimensional difference, they coassemble without phase separation, in which the resultant LC materials display essentially no deterioration of the intrinsic conducting properties.     

Structural study on 2,2'-(methylimino)bis(N,N-dioctylacetamide) complex with Re(VII)O4- and Tc(VII)O4- by 1H NMR, EXAFS, and IR spectroscopy

The structures of the complex of 2,2'-(methylimino)bis(N,N-dioctylacetamide) (MIDOA) with M(VII)O(4)(-) (M = Re and Tc), which were prepared by liquid-liquid solvent extraction, were investigated by using (1)H nuclear magnetic resonance (NMR), extended X-ray absorption fine structure (EXAFS), and infrared (IR) spectroscopy. The (1)H NMR spectra of the complex of MIDOA with Re(VII)O(4)(-) prepared in the organic solution suggest the transfer of a proton from aqueous to organic solution and the formation of the H(+)MIDOA ion. The EXAFS spectra of the complexes of H(+)MIDOA with Re(VII)O(4)(-) and Tc(VII)O(4)(-) show only the M-O coordination of the aquo complexes, suggesting that the chemical state of M(VII)O(4)(-) was unchanged during the extraction process. The results from (1)H NMR and EXAFS, therefore, provide evidence of M(VII)O(4)(-)···H(+)MIDOA complex formation in the organic solution. The IR spectra of Re(VII)O(4)(-)···H(+)MIDOA and Tc(VII)O(4)(-)···H(+)MIDOA were analyzed based on the structures and the IR spectra that were calculated at the B3LYP/cc-pVDZ level. Comparison of the observed and calculated IR spectra demonstrates that an intramolecular hydrogen bond is formed in H(+)MIDOA, and the M(VII)O(4)(-) ion interacts with H(+)MIDOA through multiple C-H(n)···O hydrogen bonds.     

π-Electron-system-layered polymer: through-space conjugation and properties as a single molecular wire

[2.2]Paracyclophane-based through-space conjugated oligomers and polymers were prepared, in which poly(p-arylene-ethynylene) (PAE) units were partially π-stacked and layered, and their properties in the ground state and excited state were investigated in detail. Electronic interactions among PAE units were effective through at least ten units in the ground state. Photoexcited energy transfer occurred from the stacked PAE units to the end-capping PAE moieties. The electrical conductivity of the polymers was estimated using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method and investigated together with time-dependent density functional theory (TD-DFT) calculations, showing that intramolecular charge carrier mobility through the stacked PAE units was a few tens of percentage larger than through the twisted PAE units.     

Readily Processable Hole‐Transporting Peropyrene Gels

The development of organic electronics requires scalable solution‐processing methods that enable the fabrication of electronic devices over large areas at low cost. The preparation of peropyrene gels constituted of 3D networks of entangled 1D ribbon‐like fibrils that extend over the μm scale are now reported. OFETs were easily fabricated by depositing the gels in the sol state over bottom‐gate bottom‐contact transistors and by allowing its gelation thereafter. Electrical characterisation of such field‐effect transistors shows a good balance between processability and performance with hole mobilities that are two orders of magnitude higher than those observed in thin films obtained from non‐gelating solvents under the same conditions.     

Charge-carrier dynamics in polythiophene films studied by in-situ measurement of flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient optical spectroscopy (TOS)

An in-situ measurement system for flash-photolysis time-resolved microwave conductivity (FP-TRMC) and transient optical spectroscopy (TOS) has been developed to perform simultaneous measurements of photo-induced changes in conductivity and charge-carrier density in an organic thin film. The electric field in the resonant cavity designed for the present system was analysed by electrostatic simulation. Using the present system and the simulated electric field, the photoconductivity and transient absorption in a regioregular poly(3-hexyl thiophene) film were measured using one particular geometry under photon excitation energies of 6.39, 4.98, 3.48, and 2.34?eV. The dynamics of photogenerated charge carriers is discussed in terms of the excitation energy and incident photon intensity. The transient absorption spectrum induced by 3.48?eV light is presented and compared with the TRMC transient.     

Transverse susceptibilities of ferromagnetic spin wave interacting with phonon reservoir, II: Temperature dependence of line shapes

A form of the transverse magnetic susceptibility of a ferromagnetic spin system with a uniaxial anisotropy energy and an anisotropic exchange interaction, interacting with a phonon reservoir, is derived in the spin-wave approximation using the TCLE method, where the phonon reservoir interacts with not only the x and y components of each spin but also its z component. The transverse magnetic susceptibility is numerically and analytically studied for the system of one-dimensional infinite spins in the lowest spin-wave approximation, by assuming a damped oscillator model of the phonon reservoir. The temperature dependence and wave number dependence of the susceptibility are numerically investigated for the half-widths and peak-heights of the line shapes in the resonance region. It is shown that as the temperature increases, the half-widths of the line shapes increase and the peak heights decrease in the resonance region, and that as the wave number increases, the half-widths of the line shapes decrease and the peak heights increase in the resonance region. It is also shown that as the uniaxial anisotropy energy of the z direction increases or as the exchange interaction between the z components of spins increases, the half-widths of the line shapes decrease and the peak heights increase in the resonance region. It is besides shown that as the characteristic frequency of the phonon increases, the line shapes show ‘motional broadening’ at the low temperature and show ‘motional narrowing’ at the high temperature. Furthermore, the resonance frequency is shown to increase as the wave number increases or as the temperature increases. The numerical results are examined analytically.     

Crystal structure and carrier transport properties of a new 3D mixed-valence Cu(I)-Cu(II) coordination polymer including pyrrolidine dithiocarbamate ligand

A novel mixed-valence Cu(i)-Cu(ii) coordination polymer having an infinite three-dimensional (3D) structure, {[Cu(I)(4)Cu(II)(2)Br(4)(Pyr-dtc)(4)]·CHCl(3)}(n) (1) (Pyr-dtc(-) = pyrrolidine dithiocarbamate), has been prepared and structurally characterized via X-ray diffraction. This complex consists of 1D Cu(i)-Br chains and bridging mononuclear copper(ii) units of Cu(II)(Pyr-dtc)(2), which form an infinite 3D network. A magnetic study indicates that this complex includes copper(ii) ions exhibiting a weak antiferromagnetic interaction (θ = -0.086 K) between the unpaired electrons of the copper(ii) ions present in the diamagnetic Cu(i)-Br chains. The carrier transport properties of 1 are investigated using an impedance spectroscopy technique and flash-photolysis time-resolved microwave conductivity measurement (FP-TRMC). The impedance spectroscopy reveals that this complex exhibits intriguing semiconducting properties at a small activation energy (E(a) = 0.29 eV (bulk)). The sum of the mobilities of the negative and positive carriers estimated via FP-TRMC is Σμ～ 0.4 cm(2) V(-1) s(-1).     

Synthesis of a head-to-tail-type cyclodextrin-based insulated molecular wire

We developed a new method for synthesizing an organic-soluble insulated molecular wire (IMW) using permethylated cyclodextrin (PMCD). The IMW obtained using this method is highly soluble in a variety of organic solvents and has a high covering ratio, regioregularity, rigidity, photoluminescence efficiency, and interchain hole mobility.     

Boronic acid-protected gold clusters capable of asymmetric induction: spectral deconvolution analysis of their electronic absorption and magnetic circular dichroism

Gold clusters protected by 3-mercaptophenylboronic acid (3-MPB) with a mean core diameter of 1.1 nm are successfully isolated, and their absorption, magnetic circular dichroism (MCD), and chiroptical responses in metal-based electronic transition regions, which can be induced by surface D-/L-fructose complexation, are examined. It is well-known that MCD basically corresponds to electronic transitions in the absorption spectrum, so simultaneous deconvolution analysis of electronic absorption and MCD spectra of the gold cluster compound is conducted under the constrained requirement that a single set of Gaussian components be used for their fitting. We then find that fructose-induced chiroptical response is explained in terms of the deconvoluted spectra experimentally obtained. We believe this spectral analysis is expected to benefit better understanding of the electronic states and the origin of the optical activity in chiral metal clusters.