TY - JOUR
T1 - Water-soluble dendrimers as photochemical reaction media
T2 - Chemical behavior of singlet and triplet radical pairs inside dendritic reaction cavities
AU - Kaanumalle, Lakshmi S.
AU - Nithyanandhan, Jayaraj
AU - Pattabiraman, Mahesh
AU - Jayaraman, Narayanaswamy
AU - Ramamurthy, V.
PY - 2004/7/28
Y1 - 2004/7/28
N2 - 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 α-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.
AB - 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 α-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.
UR - http://www.scopus.com/inward/record.url?scp=3242760589&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=3242760589&partnerID=8YFLogxK
U2 - 10.1021/ja049492w
DO - 10.1021/ja049492w
M3 - Article
C2 - 15264831
AN - SCOPUS:3242760589
VL - 126
SP - 8999
EP - 9006
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 29
ER -