title: Templating photodimerization of trans-cinnamic acid esters with a water-soluble Pd nanocage.
abstract: A water-soluble octahedral Pd nanocage acting as a reaction vessel templates the photodimerization of substituted trans-cinnamic acid methyl esters in water. Irradiation of the host-guest complexes of trans-cinnamic acid methyl esters with the Pd nanocage resulted in selective formation of a syn head-head dimer in addition to the corresponding cis isomer. These results suggest that the guest molecules are preoriented in a selective fashion with the hydrophilic ester group facing water and the hydrophobic aryl group tucked within the cavity of the host. Such an orientation occurs at the hydrophobic-hydrophilic interface between the nanocage exterior and interior. Weak intermolecular C-H-pi and pi-pi interactions between the host and the guest(s) are likely to be responsible for the lack of mobility of the reactant olefins during their short excited-state lifetime.
authors.affiliation: Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
authors.forename: S
authors.initials: S
authors.lastname: Karthikeyan
authors.forename: V
authors.initials: V
authors.lastname: Ramamurthy