Singlet-triplet interconversion of diphenylmethylene. Energetics,dynamics and reactivities of different spin states

A combination of picosecond and nanosecond laser spectroscopy measurements, chemical quenching experiments and triplet sensitization experiments has allowed the determination of the rapid singlet to triplet and slower triplet to singlet intersystem crossing rates for diphenylmethylene in fluid solution at room temperature. It is shown that under the conditions of the kinetic measurements, singlet and triplet diphenylmethylene (¹DPM and ³DPM, respectively) are in rapid equilibrium relative to reactions, so that knowledge of the values of k_ST and k_TS allows determination of the equilibrium constant and change in free energy for the ¹DPM 〈 ³DPM process. The absolute reactivity of ¹DPM toward a series of alcohols has been determined and is discussed in terms of other current investigations of carbene reactivity.     

Experimente mit Erdalkalimetallen

Reactions of the alkaline earth metals magnesium, calcium, strontium, and barium with water, phenolphthalein solution, diluted extract of red cabbage, diluted hydrochloric acid, or ammonia are well suited for a demonstration of the increase in reactivity within this group of metals with increasing atomic number. If the alkali metals lithium and sodium are included, the reactivity of six s‐block elements can be demonstrated in test tubes with small amounts of chemicals.     

EPR Studies of Tl0.5Pb0.5Sr1.6Ba0.4CaCu2?xRuxO7?δ Superconductor

Bulk superconducting samples of type Tl_0.5Pb_0.5Sr_1.6Ba_0.4CaCu_2−x Ru _x O_7−δ, (Tl, Pb)/Sr-1212, with 0.0 ≤ x ≤ 0.525 were prepared by the conventional one-step solid-state reaction technique. The prepared samples were investigated using X-ray powder diffraction, electrical resistivity and electron paramagnetic resonance (EPR) measurements. Enhancement of the phase formation, superconducting transition temperature T _c and hole carriers concentration P was observed up to x = 0.075. For x > 0.075, a reverse trend was observed. EPR spectra were measured at different temperatures (120–290 K) for all prepared samples. The number of spins N participating in the resonance and the paramagnetic susceptibility χ were calculated as a function of both Ru-content and temperature. N and χ increased as the Ru-content increased. A linear relationship between logN and 1/T was established, from which the activation energy E _a was calculated as a function of the Ru-content. The temperature dependence of χ was fitted according to Curie–Weiss type of magnetic behavior. Curie constant C, Curie temperature θ, the effective magnetic moment μ and the electronic specific heat γ were estimated as a function of the Ru-content.     

4-(Trinitromethyl)tetrahydro-2-furanol and 4-(fluorodinitromethyl)tetrahydro-2-furanol via lactone reduction with borane. The preparation of cis/trans-2-polynitroalkoxy-4-polynitromethyltetrahydrofurans

Normally borane reduces lactones too rapidly to allow the isolation of intermediates but 4-(trinitromethyl)-tetrahydro-2-furanol and 4-(fluorodinitromethyl)tetrahydro-2-furanol are isolated in 72 and 36% yield from the reduction of 4-hydroxy-3-(trinitromethyl)butyric acid, γ-lactone and 4-hydroxy-3-(fluorodinitromethyl)-butyric acid, γ-lactone with borane-tetrahydrofuran complex. The preparation of 2-polynitroalkoxy-4-polynitromethyltetrahydrofurans from the 2-furanols is described.     

From σ to π Coordination: Tetraisopropylcyclopentadienyl dichlorides [(C5HR4)ECl2] (R = CHMe2) of phosphorus,arsenic, antimony,and bismuth

[(C₅HR₄)PCl₂] ( 1a ), [(C₅HR₄)PBr₂] ( 1 b ), [(C₅HR₄)AsCl₂] ( 2 ), and [(C₅HR₄)SbCl₂] ( 3 ), have been obtained from the corresponding pnicogen trihalides and sodium tetraisopropylcyclopentadienide (R = CHMe₂). The molecular structures of 1, 2 , and 3 as well as the related structure of [(C₅HR₄)BiCl₂] ( 4 ) display increasing π character of hetero atom to cyclopentadienyl bonding with increasing metallic character of the hetero atom.     

Effect of IR laser radiation on the structure and optical properties of PC-PBT/Pd polymer nanocomposite films

ABSTRACT

Bayfol (PC-PBT blend ?lm) is a class of polymeric solid-state nuclear track detector which has a lot of applications in several radiation detection ?elds. It is a bisphenol-A polycarbonate PC blended with polybutylene terephthalate PBT. Bayfol/Palladium (PC-PBT/Pd) nanocomposite films have been deposited using the molding technique. It is worth mentioning that this report is almost the first one dealing with the topic of the changes of physical properties of Bayfol/Pd nanocomposite due to laser exposure. Samples from PC-PBT/Pd (5?wt%) nanocomposite were exposed to IR-pulsed laser of 5-W power, capable of producing 2000 pulses per second with pulse duration of 200?ns at 904?nm. The laser fluences were in the range 2–25?J/cm². The resultant modi?cations in the exposed nanocomposite samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction (XRD), UV spectroscopy and color difference studies. The results indicate the proper dispersion of Pd nanoparticles in the PC-PBT matrix that causes a strong intermolecular interaction between Pd and PC-PBT, resulted in an increase in refractive index and the amorphous phase. Also, it is found that the laser exposure reduces the optical energy gap that could be attributed to the increase in structural disorder of the exposed PC-PBT/Pd nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the exposed samples and the non-exposed one, was increased with increasing the laser fluence, convoyed by a significant increase in the green and yellow color components.