title: Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide).
abstract: Theoretical calculations have been used to examine singlet oxygen release from a naphthalene endoperoxide which bears a flexible (CH(2))(22) polymethylene "lid". Monte Carlo and ONIOM calculations that incorporated semi-empirical and density functional theory predicted the conformational influence of the polymethylene chain in the cycloreversion of dioxapaddlane, 1,4-diicosa naphthalene-1,4-endoperoxide, to (1)O(2) and 1,4-diicosa naphthalene. This study attempts to build a connection between (1)O(2) generation and "jump rope" dynamics of the dioxapaddlane. The polymethylene chain appears to function as a gatekeeper for the oxygen. Instead of coming full circle, a semi-circle rotation of the polymethylene bridge protected the peroxide group, limiting the dissociation of (1)O(2) from the naphthalene site.
authors.affiliation: Department of Chemistry and Graduate Center, Brooklyn College, The City University of New York (CUNY), Brooklyn, NY 11210, USA.
authors.forename: Alvaro
authors.initials: A
authors.lastname: Castillo
authors.forename: Alexander
authors.initials: A
authors.lastname: Greer