Solvent sensitivity of ortho substituent effect on 13C NMR chemical shift of the carboxyl carbon (δco) in benzoic acid

A reverse ortho effect is observed for the (13)C NMR chemical shifts of the carboxyl carbon (δ(co)) in benzoic acids measured in aprotic solvents of varying polarity. The ortho effect on δ(co) is best described by a combination of the reverse field and steric accelerating effects of the substituent in an 80: 20 pattern in apolar aprotic solvents and a 60: 40 pattern in dipolar aprotic ones. Interestingly, no good enough correlation was found between δ(co) and log k(1) of the acids measured in similar solvents. A critical analysis of the results clearly indicates the use of an apolar aprotic solvent and not a dipolar aprotic one as the solvent of choice for investigating intrinsic substituent effects on δ(c) in an aromatic system.     

Effect of temperature on pseudoternary system Tween-80-butanol-hexane-water

Novel periodic mesostructured organometallic silicas of MCM-41 type bearing homogeneously distributed bis(8-quinolinolato)dioxomolybdenum(VI) inside the channel walls (denoted as MoO(2)Q(2)@PMO-x) are synthesized via a convenient one-pot method and examined as catalysts in the epoxidation of cyclooctene. The ordered mesoporous structures as well as the organometallic groups incorporated into the framework are fully determined by comprehensive characterization techniques such as XRD, TEM, N(2) adsorption/desorption, SEM, FT-IR, UV-vis spectroscopy, solid-state NMR, ICP-AES, XPS and TG/DSC. MoO(2)Q(2)@PMO-6% catalyst exhibits higher activity for the epoxidation of cyclooctene with tert-butyl hydroperoxide than other MoO(2)Q(2)@PMO materials and its homogeneous or randomly grafted analogue.     

Co‐poly(aryl ether sulfone)s containing phthalimidine moiety in the main chain

Several new co‐poly(arylene ether sulfone)s have been prepared by the reaction of 4,4′‐fluorodiphenyl sulfone (FDS) with different bisphenols namely 4,4′‐isopropylidenediphenol (BPA), 4,4′‐hexafluoroisopropylidenediphenol (6F‐BPA), and N‐phenyl‐3,3‐bis(4‐hydroxyphenyl)phthalimidine(PA). The homo‐poly(arylene ether sulfone)s are named as 1a, 2a, and 3a. The copolymers namely 2b, 2c, 2d and 3b, 3c, 3d have been prepared, respectively, on reaction of FDS with BPA or 6F‐BPA using different molar ratios of PA such as 25, 50, and 75. The poly(aryl ether sulfone)s 1a containing PA unit in the main chain showed a very high glass transition temperature of 280°C and an outstanding thermal stability up to 510°C for 5% weight loss under synthetic air. Depending on the mole% of PA, the glass transition temperatures of the copolymers can be varied. The polymers were soluble in a wide range of organic solvents. Transparent thin films of these polymers exhibited tensile strengths upto 84 MPa and Young's modulus up to 3.16 GPa. The films of these polymers showed low water absorption of 0.24%. Copyright © 2009 John Wiley & Sons, Ltd.     

Fluorinated heteroaromatic polyethers for low dielectric constant / high temperature applications

Several series of poly(arylene ether)s with trifluoromethyl substituents were prepared and characterized. These materials are potential candidates for the use as low dielectric constant insulators (intermetal dielectrics, IMD, and interlayer dielectrics, ILD) on microchips. Thermal stability up to 450 °C and a dielectric constant below 3 preferably below 2.5) is required for this application. The thermal stability of the poly(arylene ether)s was increased from 320°C to more than 500 °C by optimization of the structure of the repeating unit. The dielectric constant of one of the most promising structures was determined to be 2.8. In addition, plasma polymerized thin films from hexafluorobenzene, tetrafluorobenzene, perfluorotoluene and perfluorodecaline were prepared and characterized with respect to solubility, dielectric constant, adhesion, and thermal stability.     

Photoionization Bands of Cyanogen: Multi-Mode Vibronic Coupling and Renner-Teller Effects

Multi-mode vibronic coupling in the , , and electronic states of Cyanogen radical cation (C N ) is investigated with the aid of ab initio quantum chemistry and first principles quantum dynamics methods. The electronic degenerate states of Π symmetry of C N undergo Renner-Teller (RT) splitting along degenerate vibrational modes of π symmetry. The RT split components form symmetry allowed conical intersections with those from nearby RT split states or with non-degenerate electronic states of Σ symmetry. A parameterized vibronic Hamiltonian is constructed using standard vibronic coupling theory in a diabatic electronic basis and symmetry rules. The parameters of the Hamiltonian are derived from ab initio calculated adiabatic electronic energies. The vibronic spectrum is calculated, assigned and compared with the available experimental data. The impact of various electronic coupling on the vibronic structure of the spectrum is discussed.