Pressure induced insulator-metal transition in quasi one-dimensional niobium tetraiodide

The resistivity of a quasi one-dimensional semiconductor NbI₄ was measured at high pressures. The resistivity decreased monotonously with increasing pressure. The activation energy of 0.12 eV at atmospheric pressure decreased to 0.06 eV at 100 kbar and to 0.02 eV at 130 kbar. The temperature coefficient of resistivity becomes positive at about 150 kbar.     

A novel solvent dipole-induced rotational isomerism of 1-hxdroxy-2-pyridone in the excited singlet state

The title compound shows dual fluorescence depending on polarity of the solvent used. The fluorescence in the nonpolar solvent, cyclohexane, has a maximuni at 370 nm, while the fluorescence in the polar solvent, methanol, has a maximum at 400nm. The short and long wavelength fluorescences were assigned to the syn and anti conformers, respectively. From these observations one is allowed to conclude that a novel solvent dipole-induced rotational isomerism takes place in the excited singlet state.     

Picosecond study of energy transfer between rhodamine 6G and 3,3'-diethylthiacarbocyanine iodide in the premicellar region: förster mechanism with increased local concentration

The mechanism of enhancement in the energy transfer between rhodamine 6G and 3,3'-diethylthiacarbocyanine iodide by sodium lauryl sulfate in the premicellar region was studied by a picosecond laser technique. The Forster mechanism with an increased local concentration suggesting dye-rich induced micelle formation was concluded from the shape of the decay curve.     

Analytical optimization of exponent values in protonic and deuteronic Gaussian‐type functions by elimination of translational and rotational motions from multi‐component molecular orbital scheme

To optimize the exponent values in protonic and deuteronic Gaussian‐type functions (GTF) by the elimination of translational and rotational motions, we have proposed the new scheme of an analytical gradient formula with respect to the exponent values in the multi‐component molecular orbital scheme, which can take into account the quantum effects of protons and deuterons, under the Hartree‐Fock level of theory. Numerical assessment of H₂ and D₂ molecules confirms that there is a clear difference between distributions of protonic and deuteronic orbitals following the elimination of translational and rotational motions. In particular, the d‐type GTF in the protonic orbital drastically improves the total energy. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Preparation and properties of rotaxanes formed by dimethyl-beta-cyclodextrin and oligo(thiophene)s with beta-cyclodextrin stoppers

Novel cyclodextrin rotaxanes with oligothiophene as an axis molecule have been prepared by the Suzuki coupling reaction of 6-O-(4-iodophenyl)-beta-CD (6-I-Ph-beta-CD) with di(1,3,2-dioxaborolan-2-yl)-oligothiophene (oligothiophene diboric ethylene glycol esters) in aqueous solutions of dimethyl-beta-cyclodextrin (DM-beta-CD). These reactions gave [2]rotaxanes and [3]rotaxanes, which were isolated by reversed phase chromatography. The fluorescence intensities of rotaxanes are higher than those of dumbbell-shaped molecules (without DM-beta-CD) in aqueous solutions. The inclusion ratio and chain length of rotaxanes have been found to relate to the emission properties and emission intensities of oligothiophene. In aqueous solutions, fluorescence quantum yields of rotaxanes are higher than those of dumbbell-shaped molecules. The increase in the fluorescence efficiency of rotaxane is caused by suppression of intermolecular interactions, indicating the effect of insulated oligothiophene with DM-beta-CD. beta-CD at the both ends of rotaxanes functions not only as bulky stoppers but also as the recognition site for guest molecules, as verified by fluorescence quenching experiments.     

Reversible interpenetration in a metal-organic framework triggered by ligand removal and addition

Caging cages: Crystals of a metal-organic framework, MOF-123 [Zn(7) O(2) (NBD)(5) (DMF)(2) ] have a three-dimensional porous structure in which DMF ligands (see picture, pink) protrude into small channels. Removal of these ligands triggers the transformation of this MOF to the doubly interpenetrating form, MOF-246 [Zn(7) O(2) (NBD)(5) ]. Moreover, addition of DMF into MOF-246 triggers reverse transformation to give MOF-123. NBD=2-nitrobenzene-1,4-dicarboxylate.     

Multicomponent QM study on the reaction of HOSO + NO2 with H2O: Nuclear quantum effect on structure and reaction energy profile

The hydrogen transfer reaction in the reaction of HOSO + NO₂ with and without H₂O have been investigated using multicomponent quantum-mechanics method, which can directly take nuclear quantum effect (NQE) of light nuclei into account. For the case of the reaction without H₂O, our calculation reveals that the reaction leading to trans-HONO is preferred. For the reaction with H₂O, water-non-mediated and water-mediated (hydrogen-relay) hydrogen transfer mechanism are investigated. The NQE of hydrogen nucleus lowers the relative energy of the stationary point structures and reduces the activation barrier of the reactions. The largest stabilization is found in the transition state structure of the hydrogen-relay type reaction. H/D isotope effects for the reactions are also analyzed. In particular, H/D isotope effect on the activation barrier is analyzed in detail with the aid of the active strain model.