Triplet-sensitised photolysis of the photoisomer of a 2,11-diaza[3,3](9,10) anthracenoparacyclophane: An adiabatic cycloreversion and a [2πa + 2πa + 2σs] rearrangement in a triplet state of the biplanophane system

Hideki Okamoto, Minoru Yamaji, Kyosuke Satake, Seiji Tobita, Masaru Kimura

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Abstract

The triplet-sensitized photoreactions of the title biplanophane system 6, the photoisomer of a 2,11-diaza[3,3](9,10)anthracenoparacyclophane derivative 5, were investigated by stationary and laser-flash photolyses using xanthone (XT) and benzophenone (BP) as triplet sensitizers. When photoisomer 6 underwent XT-sensitized irradiation, a triplet cyclophane 5 and a novel polycyclic product 7 were obtained via an adiabatic cycloreversion and a formal [2πa + 2πa + 2σs] rearrangement, respectively. The maximum quantum yield for the formation of cyclophane 5 (0.69) and the upper-limit efficiency for the formation of polycycle 7 (0.31) were determined by laser photolysis techniques. For BP-sensitized photolysis of photoisomer 6, oxetane 8, in addition to triplet cyclophane 5 and polycycle 7, was formed by a Paterno-Büchi reaction. The quenching rate constant (kq) of triplet BP by photoisomer 6 (3.4 × 108 dm3 mol-1 s-1) was found to be 1 order of magnitude smaller than that for XT (5.0 × 109 dm3 mol-1 s-1). On the basis of the relationship between kq and the triplet donor-acceptor energy gap, the triplet energy level of photoisomer 6 was estimated to be ∼71 kcal mol-1. The photochemical and the photophysical processes involved in the sensitized photolyses are summarized in an energetic reaction diagram and discussed in detail.

Original languageEnglish
Pages (from-to)7860-7868
Number of pages9
JournalJournal of Organic Chemistry
Volume69
Issue number23
DOIs
Publication statusPublished - Nov 12 2004

ASJC Scopus subject areas

  • Organic Chemistry

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