title: A Light-Activated Reaction Manifold.
abstract: We introduce an efficient reaction manifold where the rate of a thermally induced ligation can be controlled by a photonic field via two competing reaction channels. The effectiveness of the reaction manifold is evidenced by following the transformations of macromolecular chain termini via high-resolution mass spectrometry and subsequently by selective block copolymer formation. The light-controlled reaction manifold consists of a so-called o-quinodimethane species, a photocaged diene, that reacts in the presence of light with suitable enes in a Diels-Alder reaction and undergoes a transformation into imines with amines in the absence of light. The chemical selectivity of the manifold is controlled by the amount of ene present in the reaction and can be adjusted from 100% imine formation (0% photo product) to 5% imine formation (95% photo product). The reported light-controlled reaction manifold is highly attractive because a simple external field is used to switch the selectivity of specific reaction channels.
authors.affiliation: Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT) , Engesserstraße 18, 76128 Karlsruhe, Germany.|Institut für Biologische Grenzflächen (IBG), Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
authors.forename: Kai
authors.initials: K
authors.lastname: Hiltebrandt
authors.affiliation: Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT) , Engesserstraße 18, 76128 Karlsruhe, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Elies
authors.affiliation: Department of Chemical Engineering and Technical Chemistry, Laboratory for Chemical Technology, Ghent University , Technologiepark 914, B-9052 Gent, Belgium.|Department of Textiles, Ghent University , Technologiepark 907, B-9052 Gent, Belgium.
authors.forename: Dagmar R
authors.initials: DR
authors.lastname: D'hooge
authors.affiliation: School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT) , 2 George Street, Brisbane, QLD 4000, Australia.
authors.forename: James P
authors.initials: JP
authors.lastname: Blinco
authors.affiliation: Preparative Macromolecular Chemistry, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT) , Engesserstraße 18, 76128 Karlsruhe, Germany.|Institut für Biologische Grenzflächen (IBG), Karlsruhe Institute of Technology (KIT) , Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.|School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT) , 2 George Street, Brisbane, QLD 4000, Australia.
authors.forename: Christopher
authors.initials: C
authors.lastname: Barner-Kowollik