A laser flash photolysis study of pivalothiophenone triplets: steric and electronic effects in thione photoreaction kinetics

Upon laser pulse excitation (Aex = 532 nm) into the lowest-lying '(n,a*) band system, pivalothiophenones in benzene solutions give rise to short-lived triplets (Ama: = 325-335 nm, em: = (1 1-15) X lo3 M-' cm-I) with quantitative intersystem crossing efficiencies. The triplet yields decrease slightly (by 10-30%) upon changing A, to 308 nm (Le., upon excitation into S2). Kinetic data are presented for intrinsic triplet lifetimes, self-quenching, and quenching by oxygen, di-tert-butylnitroxy radical, and various reagents capable of interacting with the triplets via energy, electron, or hydrogen-atom transfer and by biradical formation (possibly leading to cycloaddition). The mechanisms of the quenching processes are discussed. Relative to rigid aromatic thiones, namely, xanthione and thiocoumarin, the interaction of pivalothiophenone triplets with most of the quenchers are kinetically inefficient. This is interpreted primarily as a manifestation of the steric crowding at positions a to the thiocarbonyl group.

Sequence distribution in Acrylonitrile-methylacrylate random copolymers by N.M.R spectroscopy

The sequence distribution studies on the acrylonitrile-methylmethacrylate copolymer of high methylmethacrylate (M) content (30%AMA, 2M centered units MMA (or AMM) based on the shape of the peaks observed for methixy and a-methyl protons. The presence of MMM type of triad sequences is indicated by the pattern of a-methyl protons.

Low temperature synthesis, structure and properties of alkali-doped La2NiO4, LaNiO3 and LaNi0.85Cu0.15O3 from alkali hydroxide fluxes

We report a low-temperature synthesis of La1.95Na0.05NiO4 from NaOH flux, La0.97K0.03NiO3 and La0.95K0.05Ni0.85Cu0.15O3 phases from KOH flux at 400 degreesC. Alkali-doped LaNiO3 can be prepared in KOH, but not in NaOH flux and La2NiO4 can be prepared in NaOH, but not in KOH flux. The flux-grown oxides were characterized by powder X-ray Rietveld profile analysis and electron microscopy. Sodium doped La2NiO4 crystallizes in orthorhombic structure and potassium doped LaNiO3-phases crystallizes in rhombohedral structure. La1.95Na0.05NiO4 is weakly paramagnetic and semiconducting while La0.97K0.03NiO3 and La0.95K0.05Ni0.85Cu0.15O3 show Pauli paramagnetic and metallic behavior. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.