Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

The first vapochromic organic crystals are described with respect to their preparation, color change, adsorption/desorption properties, crystal structures, and color‐change mechanism. Non‐solvatochromic, 1,4,5,8‐naphthalene‐tetracarboxylic diimide (NDI) derivatives 1 a bearing two pyrrole imine (PI) tethers have been used as a motif for the crystal packing template. Red‐purple vapochromic solid 3 was prepared by evacuation of orange crystals 2 (equivalent to 1 a ?2 MeOH), obtained by recrystallization of 1 a from MeOH. Solid 3 showed high‐adsorption ability and unprecedented vapor‐dependent color changes upon exposure to a variety of organic vapors, whereas light brown amorphous solid 1 a , did not show vapo‐ or solvatochromic behavior toward any organic solvent. The strong adsorption capability of 3 was confirmed by TGA experiments and adsorption/desorption isotherms. Analysis of the solid‐state UV/Vis analysis revealed that the vapor‐dependent color changes of 3 were owed to the specific interference of solvent vapors with its broad CT absorbance at λ=450–650 nm. Packing structures of 1 a in orange crystals 2 , red‐purple solid 3 , and regenerated orange solid 2 were unequivocally established by single crystal and synchrotron powder X‐ray diffraction, respectively. Molecular structures and arrays of 1 a in these materials indicated that 1) unit 1 a had an S‐shaped folded conformation in 2 and 3 by intramolecular donor–acceptor interactions between NDI and two PI units; 2) inclusion of the guest vapor into the S‐shaped template decreased the intramolecular PI‐NDI interactions, accompanied by increasing intermolecular NDI‐NDI and PI‐PI interactions; and 3) such flexible, open–close motions of the S‐shaped template could be repeated during reversible adsorption/desorption processes without degradation of crystal packing. The adsorption properties and mechanism of molecular shape‐dependent vapochromic behavior of 3 are discussed with reference to experimental results, crystallographic data, and theoretical calculations.     

Dynamic properties of combustion instability in a lean premixed gas-turbine combustor

We experimentally investigate the dynamic behavior of the combustion instability in a lean premixed gas-turbine combustor from the viewpoint of nonlinear dynamics. A nonlinear time series analysis in combination with a surrogate data method clearly reveals that as the equivalence ratio increases, the dynamic behavior of the combustion instability undergoes a significant transition from stochastic fluctuation to periodic oscillation through low-dimensional chaotic oscillation. We also show that a nonlinear forecasting method is useful for predicting the short-term dynamic behavior of the combustion instability in a lean premixed gas-turbine combustor, which has not been addressed in the fields of combustion science and physics.     

Measurement of Reflected and Scattered Light for Monitoring Fluctuation of Structures

A laser spectroscopic technique for studying fluctuations of structural objects is presented, together with some results of our investigations including an observation of forced vibration of a refrigerator, intrinsic vibrations of buildings, and appearance of a fluctuation in rotational speed due to fatigue. An alternative detection technique which uses the scattered light for monitoring in place of the mirror-reflected beam is also presented. A leak of water out of a pipeline was detected with this method.

The results obtained with this laser spectroscopic technique should form a useful collection of data regarding fluctuation analysis of various objects.     

Switchable C- and N-bound isomers of transition-metal cyanocarbanions: synthesis and interconversions of cyclopentadienyl ruthenium complexes of phenylsulfonylacetonitrile anions

The synthesis, structure, and dynamic behavior of bistable C- and N-bound isomers of transition-metal cyanocarbanions are described. A series of C-bound cyclopentadienyl (Cp) ruthenium phosphane complexes, [Ru{CH(CN)SO2Ph}(Cp)L1L2] (3), and their N-bound isomers, [Ru+(Cp)(NCCH(-)SO2Ph)L1L2] (4), were prepared by treating [RuCl(Cp)(PR3)2] with the sodium salt of phenylsulfonylacetonitrile and performing ligand-exchange reactions with the resulting compounds. Structural characterization by X-ray diffraction indicates that the cyanocarbanion moiety of 3 has an alpha-metalated structure, whereas that of 4 has a zwitterionic, end-on structure. Heating these complexes in aprotic solvents gives rise to irreversible linkage isomerization between C- and N-bound isomers, in which the relative thermal stabilities vary greatly depending on the steric and electronic nature of the ligands. Mechanistic studies of N-to-C isomerization revealed that the reaction proceeds irreversibly in a unimolecular manner without the formation of coordinatively unsaturated species. A metal-sliding process, which occurs over the -C-C triple chemical bond N pi-conjugated surface of the cyanocarbanion moiety, was suggested by results from kinetic studies and density functional theory (DFT) calculations. C-to-N isomerizations proceed by the above-mentioned intramolecular process, with a temperature-dependent contribution from the formation and cleavage of mu2-C,N coordination dimers [{Ru{CH(CN)SO2Ph}(Cp)(PPh3)}2] (15 and 16).     

Ion-Channel – Mimetic Sensors Based on Self-Assembled Monolayers of Phosphate Esters: High Selectivity for Trivalent Cations

 Gold electrodes were chemically modified with a phosphate ester monolayer designed to mimic biological ion-channel membranes. Cyclic voltammograms of Fe(CN)₆ ³⁻ as electroactive marker were measured in the presence of various types of analyte cations. Whereas in the absence of analyte cations the marker reduction was hindered by electrostatic repulsion between the marker anions and phosphate groups of the receptor monolayer, binding of di-and trications to the monolayer resulted in large increases of the reduction current. Trivalent cations could be detected down to the submicromolar concentration range with excellent selectivities over alkali metal ions. Also divalent cations were well discriminated and similar responses as to trivalent cations were only observed if their concentration exceeded that of the trivalent cations by about two orders of magnitudes. Received August 24, 1998. Revision March 10, 1999.     

A ferroelectric barium titanate,BaTi2O5

The crystal structure of monobarium dititanium pentaoxide, BaTi₂O₅, synthesized by a floating‐zone method, was studied by X‐ray diffraction. Previous reports describe the structure as being in the monoclinic centrosymmetric space group C2/m. We have recently found that this material exhibits ferroelectricity, and therefore BaTi₂O₅ should have lower symmetry. The crystal structure of BaTi₂O₅ was refined in space group C2, revealing a displacement of the Ti atoms along the b axis. This result is consistent with the fact that the ferroelectricity of BaTi₂O₅ was only observed along the b axis.     

Rheological and DSC studies of mixtures of gellan gum and konjac glucomannan

The interaction between gellan gum (GELL) and konjac glucomannan (KGM) with and without sodium chloride, potassium chloride, calcium chloride and magnesium chloride has been monitored using mechanical spectroscopy and differential scanning calorimetry (DSC). The rheological results indicated that the synergism occurred at sufficient low temperatures where individual helices of GELL molecules were sufficiently aggregated. With progressive addition of monovalent cations, storage shear modulus G' and loss shear modulus G” for mixtures gradually increased, and not only the helix-coil transition temperature of GELL molecules in mixtures but also the sol-gel transition temperature for mixtures shifted to higher temperatures with increasing concentration of salts. Moreover, in the presence of sufficient monovalent cations, mixtures formed an elastic gel with large thermal hysteresis. In the presence of divalent cations, the synergistic interaction was promoted up to a certain concentration, however, with more progressive addition of divalent cations, the main structure formed by aggregates of GELL helices would be smaller, so that mixtures could not form a gel in the presence of excessive divalent cations. DSC results indicated that the intermolecular binding complexes between GELL and KGM molecules would not occur, but KGM markedly influenced the disorder-order transition of GELL molecules. We have suggested that KGM was attached to the surface of large aggregates of GELL helices, and since cations promote GELL self-aggregation by a screening effect, the synergistic interaction between GELL and KGM was promoted with increasing concentration of salts. However, excessive divalent cations formed various aggregates of GELL helices with different thermal stabilities, so that the phase-separation in GELL/KGM mixtures was promoted in the presence of excessive divalent cations.     

In situ hydrogenation of terminal halogen in poly(methyl methacrylate) by ruthenium-catalyzed living radical polymerization: direct transformation of "polymerization catalyst" into "hydrogenation catalyst"

An in situ, selective, and quantitative hydrogenation of the terminal chlorine (alpha-haloester) in living PMMA-Cl into PMMA-H was achieved via direct transformation of a "polymerization catalyst" into a "hydrogenation catalyst" in the Ru(II)-catalyzed living radical polymerization, where the polymerization mixture of MMA was directly treated in situ with K2CO3 as a base and 2-propanol as a hydrogen donor. The reaction terminated the polymerization and, more importantly, the terminal chlorine was quantitatively hydrogenated, as confirmed by SEC, 1H NMR, and MALDI-TOF MS.