Proton Conduction at High Temperature in High-Symmetry Hydrogen-Bonded Molecular Crystals of RuIII Complexes with Six Imidazole-Imidazolate Ligands

A new H-bonded crystal [Ru^III(Him)₃(Im)₃] with three imidazole (Him) and three imidazolate (Im⁻) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the Ru^III complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10⁻⁵ S cm⁻¹ at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [Ru^III(Him)₃(Im)₃] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state ²H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered.     

Syntheses and properties of dumbbell‐shaped POSS derivatives linked by luminescent π‐conjugated units

Dumbbell‐shaped isobutyl‐substituted 1,2‐bis(4‐vinylphenyl)acetylene‐linked POSS (DA1), 9,10‐bis(4‐vinylphenyl)ethynyl)anthracene‐linked POSS (DA2), and 5,5″‐bis((4‐vinyl)phenyl)ethynyl)‐2,2′:5′2″‐terthiophene‐linked POSS (DA3), and corresponding model compounds were synthesized by cross metathesis and Sonogashira reaction, and their film formability, and thermal and optical properties were examined. The dumbbell structures of the obtained compounds were confirmed by ¹H‐, ¹³C‐, and ²⁹Si‐NMR and MALDI‐TOF‐MS analysis. The dumbbell‐shaped POSS compounds gave optically transparent films. All the model compounds, however, formed opaque films. All the films were emissive under UV irradiation. The dumbbell structures minimize longer wavelength shifts and improve emission efficiency of the luminescent π‐conjugated linker units in their solid states compared with the model compounds. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012.     

Synthesis of water-soluble C60-porphyrin hybrid compounds

Water-soluble C60-porphyrin hybrid molecules were first synthesized toward their pharmaceutical applications.     

Nuclear magnetic resonance spectra of carbanions—VI. Cumyl-, α-methylbenzyl- and benzyl carbanions

The proton magnetic resonance spectra of the three title carbanions have been observed in THF with potassium as a counter ion. The ortho-protons in the α-methylbenzyl carbanion are nonequivalent at room temperature. This shows that the α-carbon in this carbanion is in the near-sp² configuration. The aromatic proton chemical shifts of the benzylpotassium obtained here are at higher shielding than those of benzyllithium reported previously by Sandel and Freedman. This seems to arise from the different ionic nature of the bonds between carbon and metal in the carbanions.     

Observation of the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot

We have observed the Fano-Kondo antiresonance in a quantum wire with a side-coupled quantum dot. In a weak coupling regime, dips due to the Fano effect appeared. As the coupling strength increased, conductance in the regions between the dips decreased alternately. From the temperature dependence and the response to the magnetic field, we conclude that the conductance reduction is due to the Fano-Kondo antiresonance. At a Kondo valley with the Fano parameter q approximately 0, the phase shift is locked to pi/2 against the gate voltage when the system is close to the unitary limit in agreement with theoretical predictions by Gerland et al. [Phys. Rev. Lett. 84, 3710 (2000)].     

Observation of "partial coherence" in an Aharonov-Bohm interferometer with a quantum dot

We report experiments on the interference through spin states of electrons in a quantum dot (QD) embedded in an Aharonov-Bohm (AB) interferometer. We have picked up a spin-pair state, for which the environmental conditions are ideally similar. The AB amplitude is traced in a range of gate voltage that covers the pair. The behavior of the asymmetry in the amplitude around the two Coulomb peaks agrees with the theoretical prediction that the spin-flip process in a QD is related to the quantum dephasing of electrons. These results constitute evidence of "partial coherence" due to an entanglement of spins in the QD and in the interferometer.     

Luminescence channels of manganese-doped spinel

Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl₂O₄. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state ⁴T₁ to the ground state ⁶A₁ of Mn²⁺ (3d)⁵ ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion.     

Direct observation of chiral susceptibility in the canonical spin glass AuFe

The extraordinary Hall resistivity rho(xy) and the magnetization M of a canonical spin glass AuFe (8 at.% Fe) were measured simultaneously as functions of temperature with the best care to the thermal and the magnetic field hysteresis. The data of rho(xy) show an anomaly at the spin glass transition temperature T(g) and have different zero field cooling (ZFC) and field cooling (FC) measurements below T(g). Moreover, the value of rho(xy)/M, which represents the chiral susceptibility of the system in the present case, also shows the difference between ZFC and FC measurements. The results are consistent with the predictions of the chirality scenario of canonical spin glasses by Kawamura.     

Nonlinear whispering-gallery modes in a microellipse cavity

We study theoretically the effect of deformed microelliptical cavities on lasing characteristics. We show that the transition of stationary lasing states from unidirectional rotational waves to a mixture of clockwise and anticlockwise rotational waves occurs when the shape of a disk is deformed to that of an ellipse.