A novel type of metal‐containing polyimides based on tricarbonylrhenium(I) diimine complexes

A series of rhenium containing polyimides was prepared by the polymerization between a tricarbonylrhenium diimine complex with various aromatic dianhydrides. Electronic absorption spectra of the polymers showed a very strong intramolecular charge transfer transition which obscures the transfer transition band due to the rhenium complex in the visible region. A large photocurrent response was also observed when the polyimide was irradiated at 514 nm.     

Specificity in Chemical Perturbation of Crystal Structures

The specificity in chemical perturbation of crystal structure is examined by investigating the efffect of the position of particular substituent group on the crystal structure. 1,2,3,5-tetra-halobenzenes are chosen for this study. A comparative study of Raman phonon spectra of 1,2,3,5-tetrachlorobenzene; 1,2,3-trichloro-5-bromobenzene; and 1,3,5-trichloro-2-bromo-benzene crystals reveals that former two have the same crystal structure, while the latter has a different crystal structure. It is inferred that a bromine group substitution in 2-position of 1,2,3,5-tetrachlorbenzene creates a lattice instability which gives rise to a different crystal structure for 1,3,5-trichloro-2-bromobenzene. The nature of this instability is discussed. Mixed crystals of 1,2,3,5-tetrachlorobenzene and 1,2,3-trichloro-5-bromobenzene are studied to establish phonon correlation and deloalization.     

Electronic transmission of three-terminal pyrene molecular bridge

This paper investigates theoretically the electronic transmission spectra of the three terminal pyrene molecular bridge and the quantum current distribution on each bond by the tight-binding model based on nonequilibrium Green's function and the quantum current density approach, in which one π molecular orbital is taken into account per carbon atom when the energy levels and HOMO-LUMO gap are obtained. The transmission spectra show that the electronic transmission of the three terminal pyrene molecular bridge depends obviously on the incident electronic energy and the pyrene eigenenergy. The symmetrical and oscillation properties of the transmission spectra are illustrated. A novel plus-minus energy switching function is found. The quantum current distribution shows that the loop currents inside the pyrene are induced, and some bond currents are much larger than the input and the output currents. The reasons why the loop currents and the larger bond currents are induced are the phase difference of the atomic orbits and the degeneracy of the molecular orbits. The calculations illustrate that the quantum current distributions are in good agreement with Kirchhoff quantum current conservation law.     

Tunable photonic Bloch oscillations in electrically modulated photonic crystals

We exploit theoretically the occurrence and tunability of photonic Bloch oscillations (PBOs) in one-dimensional photonic crystals (PCs) containing nonlinear composites. Because of the enhanced third-order nonlinearity (Kerr-type nonlinearity) of composites, photons undergo oscillations inside tilted photonic bands, which are achieved by the application of graded external-pump electric fields on such PCs, varying along the direction perpendicular to the surface of layers. The tunability of PBOs (including amplitude and period) is readily achieved by changing the field gradient. With an appropriate graded pump ac or dc electric field, terahertz PBOs can appear and cover a terahertz band in an electromagnetic spectrum.     

Organic reactions in frozen water: Michael addition of amines and thiols to the dehydroalanine side chain of nocathiacins

Nocathiacins are densely functionalized cyclic thiazolyl peptide natural products with potent in vitro and in vivo antibacterial activity against a variety of gram-positive bacteria, including a number of multiple drug-resistant strains. Attempts to prepare Michael adducts using known conditions resulted in the formation of complex mixture of products. In order to overcome this problem, we developed unique conditions in which Michael addition of amine and thiol nucleophiles to the dehydroalanine moiety of nocathiacins was successfully achieved in frozen water. Under these conditions, the Michael addition was highly chemoselective, very efficient and provided good isolated yields of the desired products.     

Computation of deuterium isotope perturbation of 13C NMR chemical shifts of alkanes: a local mode zero-point level approach

Replacement of H by D perturbs the (13)C NMR chemical shifts of an alkane molecule. This effect is largest for the carbon to which the D is attached, diminishing rapidly with intervening bonds. The effect is sensitive to stereochemistry and is large enough to be measured reliably. A simple model based on the ground (zero point) vibrational level and treating only the C-H(D) degrees of freedom (local mode approach) is presented. The change in CH bond length with H/D substitution as well as the reduction in the range of the zero-point level probability distribution for the stretch and both bend degrees of freedom are computed. The (13)C NMR chemical shifts are computed with variation in these three degrees of freedom, and the results are averaged with respect to the H and D distribution functions. The resulting differences in the zero-point averaged chemical shifts are compared with experimental values of the H/D shifts for a series of cycloalkanes, norbornane, adamantane, and protoadamantane. Agreement is generally very good. The remaining differences are discussed. The proton spectrum of cyclohexane- is revisited and updated with improved agreement with experiment.     

Tunable hybridization at midzone and anomalous Bloch-Zener oscillations in optical waveguide ladders

We have studied the optical oscillation and tunneling of light waves in optical waveguide ladders (OWLs) formed by two coupled planar optical waveguide arrays. For the band structure, a midzone gap is formed owing to band hybridization, and its wavenumber position can be tuned throughout the whole Brillouin zone, which is different from the Bragg gap. By imposing a gradient in the propagation constant in each array, Bloch-Zener oscillation (BZO) is realized with Zener tunneling between the bands occurring at the midzone, which is contrary to the common BZO with tunneling at the center or edge of the Brillouin zone. The occurrence of BZO is demonstrated by using the field-evolution analysis. The tunable hybridization at the midzone enhances the tunability of BZO in the OWLs. This Letter may offer new insights into the coherent phenomena in optical lattices.