title: Photochemistry and Transmission Pump-Probe Spectroscopy of 2-Azidobiphenyls in Aqueous Nanocrystalline Suspensions: Simplified Kinetics in Crystalline Solids.
abstract: Aqueous nanocrystalline suspensions provide a simple and efficient medium for performing transmission spectroscopy measurements in the solid state. In this Letter we describe the use of laser flash photolysis methods to analyze the photochemistry of 2-azidobiphenyl and several aryl-substituted derivatives. We show that all the crystalline compounds analyzed in this study transform quantitatively into carbazole products via a crystal-to-crystal reconstructive phase transition. While the initial steps of the reaction cannot be followed within the time resolution of our instrument (ca. 8 ns), we detected the primary isocarbazole photoproducts and analyzed the kinetics of their formal 1,5-H shift reactions, which take place in time scales that range from a few nanoseconds to several microseconds. It is worth noting that the high reaction selectivity observed in the crystalline state translates into a clean and simple kinetic process compared to that in solution.
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Tim S
authors.initials: TS
authors.lastname: Chung
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Anoklase J-L
authors.initials: AJ
authors.lastname: Ayitou
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Jin H
authors.initials: JH
authors.lastname: Park
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Vanessa M
authors.initials: VM
authors.lastname: Breslin
authors.affiliation: Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095-1569, United States.
authors.forename: Miguel A
authors.identifier: http://orcid.org/0000-0002-6268-1943
authors.initials: MA
authors.lastname: Garcia-Garibay