Second-order Coriolis resonance between ν2 and ν5 of CH3F by microwave spectroscopy

The J = 1 ← 0 and J = 2 ← 1 transitions and the l-doubling transitions of J = 2 – 6 of ¹²CH₃F in the ν₂ and ν₅ states were analyzed by taking into account the Coriolis interaction between the two modes. The molecular constants which are derived are: ν₅ - ν₂, 252 412 ± 112; $\text{B}{}_5{}^1$, 25 611.60 ± 0.40; A_ζ5, ?38 772 ± 116; $\text{B}{}_2{}^1$, 25 432.52 ± 0.33; D, 21 838.4 ± 8.2; $\text{q}{}_5{}^1$, 39.58 ± 0.30 MHz; in addition to a few other minor constants. The present result is completely consistent with the recent Raman data of Escribano, Mills, and Brodersen, J. Mol. Spectrosc.61, 249 (1976). Molecular constants in the ν₃ and ν₆ states have also been obtained: B₃, 25 197.570 ± 0.020; B₆, 25 418.917 ± 0.047; A_ζ6ηJ, ?0.562 ± 0.030; |q₆|, 8.70 ± 0.13 MHz. Errors are 2.5 times the standard deviations.     

Analysis of creep due to grain-boundary diffusion in hexagonal microstructures

For steady-state deformation caused by grain-boundary diffusion in hexagonal microstructures, the stress distribution on grain boundaries and the macroscopic strain rates are analysed by taking the effects of viscous grain-boundary sliding into account. The maximum normal stress and the extent of stress concentration are shown to decrease as the grain-boundary viscosity increases. For infinite viscosity and/or extremely small grain sizes, the distribution of the normal stress becomes uniform on grain boundaries. The strain rates are predicted by both the stress analysis and the energy balance method, and the two strain rates are consistent with each other. The predicted strain rates also decrease as the grain-boundary viscosity increases. The present analysis reveals that the grain-size exponent is dependent on the grain size and the grain-boundary viscosity: the exponent becomes unity for small grain sizes and/or high viscosity, while it is three for large grain sizes and/or low viscosity. Recent experimental observations that the strain rates of nano-sized grain are much lower than those predicted by grain-boundary diffusion are explained by the increasing contribution of viscous grain-boundary sliding with decreasing grain size.     

Electronic structure of the organic conductors based on BMDT-TTF (BIS(methylenedithio)tetrathiafulvalene)

In the crystals of the cation radical salts based on the organic donor BMDT-TTF, the charge separation is observed. This comes from (1) nonequivalency of the site potential and (2) the long range electron-electron interaction, which are related to the two-dimensional nature of the molecular arrangement. The effects of the charge separation on the elctronic structure are discussed.     

Alkyl Ammonium Ion Selectivity of Hexahomotrioxacalix[3]arene Triamide Derivative having the Intramolecular Hydrogen-Bonding Group

The lower rim functionalized hexahomotrioxacalix[3]arene triamide 4 with cone-conformation was synthesized from triol 1 by a stepwise reaction. The different extractability for alkali metal ions, transition metal ions, and alkyl ammonium ions from water into dichloromethane is discussed. Due to the strong intramolecular hydrogen bonding between the neighboring NH and CO groups in triamide 4, its affinity to metal cations was weakened. Triamide 4 shows a single selectivity to n-BuNH ₃ ⁺ . The anion complexation of triamide 4 was also studied by ¹H NMR titration experiments. Triamide 4 binds halides through the intermolecular hydrogen bonding among the NH hydrogens of amide in a 1:1 fashion in CDCl₃. The association constants calculated from these changes in chemical shifts of the amide protons are K _a = 223 M^?1 for Cl^? and K _a = 71.7 M^?1 for Br^?. Triamide 4 shows a preference for Cl^? complexation than Br^? complexation.     

An efficient novel synthesis of beta-(azuleno[1,2-b]benzothienyl)- and beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones by the tropylium ion-mediated intramolecular furan ring-opening reaction and X-ray investigation of methyl ketone derivative

Intramolecular reaction of 2-tropylio-3-(5-substituted 2-furyl)benzothiophenes (3), prepared from the corresponding 2-cycloheptatrienyl-3-(5-substituted 2-furyl)benzothiophenes (2), afforded the beta-(azuleno[1,2-b]benzothienyl)-alpha,beta-unsaturated ketones (4), which are otherwise difficult to obtain, in moderate yields. The reaction involves a ring-opening process of the furan ring by intramolecular attack of the tropylium ion onto the 2-position of the furan ring. Similarly, beta-(azuleno[2,1-b]benzothienyl)-alpha,beta-unsaturated ketones (8) were obtained from the corresponding 3-tropylio-2-(5-substituted 2-furyl)benzothiophenes (7) albeit in lower yields. The molecular and crystal structures of the methyl ketone derivative, 8a, are discussed on the basis of X-ray structure analysis.     

Click-modified hexahomotrioxacalix[3]arenes as fluorometric and colorimetric dual-modal chemosensors for 2,4,6-trinitrophenol

A new type of chemosensor-based approach to the detection of 2,4,6-trinitrophenol (TNP) is described in this paper. Two hexahomotrioxacalix[3]arene-based chemosensors 1 and 2 were synthesized through click chemistry, which exhibited high binding affinity and selectivity toward TNP as evidenced by UV–vis and fluorescence spectroscopy studies. ¹H NMR titration analysis verified that CH?O hydrogen bonding is demonstrated as the mode of interaction, which possibly facilitates effective charge-transfer.