title: Water-soluble dendrimers as photochemical reaction media: chemical behavior of singlet and triplet radical pairs inside dendritic reaction cavities.
abstract: Water-soluble poly(alkyl aryl ether) dendrimers have been explored for their use as hosts of organic substrates in aqueous media. Prototypical photoreactions, namely, photo-Fries reaction of (a) 1-naphthyl benzoate and (b) 1-naphthyl phenyl ester and alpha-cleavage reaction of (a) dibenzyl ketones and (b) benzoin alkyl ethers, have been examined. We find that a dendritic microenvironment not only restricts the mobility of radical intermediates but also rigidly encapsulates the substrate, intermediates, and products from "leaking" to the bulk environment. Comparative studies of the same photoreactions in micellar media demonstrate that dendritic media offer much better constrainment than the micelles.
authors.affiliation: Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
authors.forename: Lakshmi S
authors.initials: LS
authors.lastname: Kaanumalle
authors.forename: Jayaraj
authors.initials: J
authors.lastname: Nithyanandhan
authors.forename: Mahesh
authors.initials: M
authors.lastname: Pattabiraman
authors.forename: Narayanaswamy
authors.initials: N
authors.lastname: Jayaraman
authors.forename: V
authors.initials: V
authors.lastname: Ramamurthy