title: Role of free space and conformational control on photoproduct selectivity of optically pure α-alkyldeoxybenzoins within a water-soluble organic capsule.
abstract: Optically pure α-alkyl deoxybenzoins resulting in products of Norrish Type I and Type II reactions upon excitation has been investigated within the octa acid (OA) capsule in water. The product distribution was different from that in an organic solvent and was also dependent on the length of the α-alkyl chain. Most importantly, a rearrangement product not formed in an organic solvent arising from the triplet radical pair generated by Norrish Type I reaction was formed, and its yield was dependent on the alkyl chain length. In an organic solvent, since the cage lifetime is shorter than the time required for intersystem crossing (ISC) of the triplet radical pair to the singlet radical pair the recombination with or without rearrangement of the primary radical pair (phenylacetyl and benzyl) does not occur. Recombination without rearrangement within the capsule as inferred from monitoring the racemization of the optically pure α-alkyl deoxybenzoins suggesting the capsule's stability for at least 10(-8) s (the time required for ISC) is consistent with our previous photophysical studies that showed partial opening and closing of the capsule in the time range of microseconds.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
authors.forename: Revathy
authors.initials: R
authors.lastname: Kulasekharan
authors.forename: Murthy V S N
authors.initials: MV
authors.lastname: Maddipatla
authors.forename: Anand
authors.initials: A
authors.lastname: Parthasarathy
authors.forename: V
authors.initials: V
authors.lastname: Ramamurthy