93433-55-7Relevant articles and documents
Structure-Kinetics Correlations in Isostructural Crystals of α-(ortho-Tolyl)-acetophenones: Pinning Down Electronic Effects Using Laser-Flash Photolysis in the Solid State
Ayitou, Anoklase J.-L.,Flynn, Kristen,Jockusch, Steffen,Khan, Saeed I.,Garcia-Garibay, Miguel A.
, p. 2644 - 2648 (2016/03/12)
Aqueous suspensions of nanocrystals in the 200-500 nm size range of isostructural α-(ortho-tolyl)-acetophenone (1a) and α-(ortho-tolyl)-para-methylacetophenone (1b) displayed good absorption characteristics for flash photolysis experiments in a flow system, with transient spectra and decay kinetics with a quality that is similar to that recorded in solution. In contrast to solution measurements, reactions in the solid state were characterized by a rate limiting hydrogen transfer reaction from the triplet excited state and a very short-lived biradical intermediate, which does not accumulate. Notably, the rate for δ-hydrogen atom transfer of 1a (2.7 × 107 s-1) in the crystalline phase is 18-fold larger than that of 1b (1.5 × 106 s-1). With nearly identical molecular and crystal structures, this decrease in the rate of δ-hydrogen abstraction can be assigned unambiguously to an electronic effect by the para-methyl group in 1b, which increases the contribution of the 3π,π? configuration relative to the reactive 3n,π? configuration in the lowest triplet excited state. These results highlight the potential of relating single crystal X-ray structural data with absolute kinetics from laser flash photolysis.
Compounds affecting the central nervous system. V. Substituted 3-dialkylaminoalkylindenes.
Bavin,Ganellin,Loynes,Spickett
, p. 513 - 516 (2007/10/06)
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