title: Triggered exchange of anionic for neutral guests inside a cationic coordination cage.
abstract: Molecular encapsulation processes under the control of an external trigger play a major role in biological signal transduction processes and enzyme catalysis. Here, we present an artificial mimic of a controllable host system that forms via self-assembly from a simple bis-monodentate ligand and Pd(II) cations. The resulting interpenetrated double cage features three consecutive pockets which initially contain one tetrafluoroborate anion, each. Activation of this host system with two halide anions triggers a conformational change that renders the central pocket susceptible to the uptake of small neutral guest molecules. Thereby, the pentacationic cage expels the central anion and replaces it with a neutral molecule to give a hexacationic species. The cage structures prior and after the halide triggered binding of benzene were examined by X-ray crystallography, ESI MS, and NMR techniques. The kinetics and thermodynamics of the encapsulation of benzene, cyclohexane, and norbornadiene are compared.
authors.affiliation: Institute of Inorganic Chemistry, Georg-August-University Göttingen , Tammannstraße 4, 37077 Göttingen, Germany.
authors.forename: Susanne
authors.initials: S
authors.lastname: Löffler
authors.forename: Jens
authors.initials: J
authors.lastname: Lübben
authors.forename: Lennard
authors.initials: L
authors.lastname: Krause
authors.forename: Dietmar
authors.initials: D
authors.lastname: Stalke
authors.forename: Birger
authors.initials: B
authors.lastname: Dittrich
authors.forename: Guido H
authors.initials: GH
authors.lastname: Clever