Intermolecular Electron Spin Transfer between Naphthalene π-Systems Separated by a Variable Number of Spirobonded Cyclobutane Rings,An. ESR and ENDOR Study

The radical anions of the compounds N1N, N3N and N5N , in which two naphthalen π-systems are separated by 1, 3 and 5 spirobonded cyclobutane rings, respectively, and tha tof the reference compound N1 , containing one naphthalene π-system and one cyclobutane ring, have been studied by ESR and ENDOR spectroscopy under a variety of experimental conditions. The intramolecular electrons spin transfer between the two π-moieties in N3N and N5N is slow on the hyperfine time-scale, irrespective of the applied conditions. It is also slow in N1N , except for media of high solvating power. In such media, with a slight reduction of N1N to its radical anion, a paramagnetic species is observed, the hyperfine data for which are consistent with N1N to its radical anion, a paramagnetic species is observed, the hyperfine data of which are consistent with N1N , undergoing a fast intramolecular electron spin tansfer. The ESR and ENDOR spectra of this species are superimposed on those characteristic of a slow transfer. It is suggested that the fast and slow transfer involve the syn- and anti-conformations, respectively, since the distance, r, between the two naphthalene π-systems of N1N is considerably shorter in the former than in the latter (r = 740 vs. 880 Pm for the distance between the centres of the π-systems). Glassy solutions of exhaustively reduced N1N display signals of the dianion triplet state, whereas no such signals are found for N3N and N5N . The zero-field splitting parameter, D , is 4.7 mT, corresponding to r ≈ 480 pm.     

Fano factor reduction on the 0.7 conductance structure of a ballistic one-dimensional wire

We have measured the nonequilibrium current noise in a ballistic one-dimensional wire which exhibits an additional conductance plateau at 0.7x2e(2)/h. The Fano factor shows a clear reduction on the 0.7 structure, and eventually vanishes upon applying a strong parallel magnetic field. These results provide experimental evidence that the 0.7 structure is associated with two conduction channels that have different transmission probabilities.     

Possible evidence of a spontaneous spin polarization in mesoscopic two-dimensional electron systems

We have experimentally studied the nonequilibrium transport in low-density clean two-dimensional (2D) electron systems at mesoscopic length scales. At zero magnetic field (B), a double-peak structure in the nonlinear conductance was observed close to the Fermi energy in the localized regime. From the behavior of these peaks at nonzero B, we could associate them with the opposite spin states of the system, indicating a spontaneous spin polarization at B=0. Detailed temperature and disorder dependence of the structure shows that such a splitting is a ground-state property of low-density 2D systems.     

Minimum dissipative relaxed states in toroidal plasmas

Relaxation of toroidal discharges is described by the principle of minimum energy dissipation together with the constraint of conserved global helicity. The resulting Euler-Lagrange equation is solved in toroidal coordinates for an axisymmetric torus by expressing the solutions in terms of Chandrasekhar-Kendall (C-K) eigenfunctions analytically continued in the complex domain. The C-K eigenfunctions are obtained as hypergeometric functions that are solutions of scalar Helmholtz equation in toroidal coordinates in the large aspect-ratio approximation. Equilibria are constructed by assuming the current to vanish at the edge of plasma. For the m=0, n=0 (m and n are the poloidal and toroidal mode numbers respectively) relaxed states, the magnetic field, current, q (safety factor) and pressure profiles are calculated for a given value of aspect-ratio of the torus and for different values of the eigenvalue λ _{r 0}. The new feature of the present model is that solutions allow for both tokamak as well as RFP-like behaviour with increase in the values of λ _{r 0}, which is related directly to volt-sec in the experiment.     

Optical control of the mobility of a MODFET with a layer of self-assembled quantum dots

We report an experimental study of GaAs/Al_0.33Ga_0.67As modulation doped field effect (MODFET) transistors, in which an InAs layer of self-assembled quantum dots is placed in one of the Al_0.33Ga_0.67As barrier layers close to the two-dimensional electron gas (2DEG). We find the source–drain resistance is bistable with the two states controlled by illumination and applied gate bias. Brief illumination induces a large, persistent drop in the resistance, which can be recovered by applying a positive gate bias. Magneto-transport measurements show that while illumination causes only a relatively small change in the 2DEG density, it can greatly enhance its mobility. We suggest this is because the 2DEG mobility is limited by percolation of the electrons through the rough electrostatic potential induced by the charged dots. Illumination reduces the negative charge trapped in the dots, thus smoothing the conduction band potential, which produces a large increase in the mobility.     

Evidence for charging effects in an open dot at zero magnetic field

We have measured the low-temperature transport properties of an open quantum dot formed in a clean one-dimensional channel. At zero magnetic field, continuous and periodic oscillations superimposed upon ballistic conductance steps are observed when the conductance through the dot G exceeds 2e²/h. We ascribe the observed conductance oscillations to evidence for charging effects in an open dot. This is supported by the evolution of the oscillating features for G>2e²/h as a function of both temperature and barrier transparency.     

Effect of supercritical CO2 on the copolymerization behavior of cyclohexene oxide/CO2 and copolymer properties with DMC/Salen‐Co(III) catalyst system

The copolymerization of cyclohexene oxide (CHO) and carbon dioxide (CO₂) was carried out under supercritical CO₂ (scCO₂) conditions to afford poly (cyclohexene carbonate) (PCHC) in high yield. The scCO₂ provided not only the C1 feedstock but also proved to be a very efficient solvent and processing aid for this copolymerization system. Double metal cyanide (DMC) and salen‐Co(III) catalysts were employed, demonstrating excellent CO₂/CHO copolymerization with high yield and high selectivity. Surprisingly, our use of scCO₂ was found to significantly enhance the copolymerization efficiency and the quality of the final polymer product. Thermally stable and high molecular weight (MW) copolymers were successfully obtained. Optimization led to excellent catalyst yield (656 wt/wt, polymer/catalyst) and selectivity (over 96% toward polycarbonate) that were significantly beyond what could be achieved in conventional solvents. Moreover, detailed thermal analyses demonstrated that the PCHC copolymer produced in scCO₂ exhibited higher glass transition temperatures (T_g ～ 114 °C) compared to polymer formed in dense phase CO₂ (T_g ～ 77 °C), and hence good thermal stability. Additionally, residual catalyst could be removed from the final polymer using scCO₂, pointing toward a green method that avoids the use of conventional volatile organic‐based solvents for both synthesis and work‐up. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2785–2793