title: Modulating the binding of polycyclic aromatic hydrocarbons inside a hexacationic cage by anion-π interactions.
abstract: We report the template-directed synthesis of BlueCage(6+), a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron-poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage⋅6 PF6 exhibits a lower association constant Ka than its progenitor ExCage⋅6 PF6. A close inspection reveals that the six PF6(-) counterions of BlueCage(6+) occupy the cavity in a fleeting manner as a consequence of anion-π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the Ka value for pyrene in BlueCage(6+) when the PF6(-) counterions are replaced by much bulkier anions. The presence of anion-π interactions is supported by X-ray crystallography, and confirms the presence of a PF6(-) counterion inside its cavity.
authors.affiliation: Center for the Chemistry of Integrated Systems, Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (USA).
authors.forename: Nema
authors.initials: N
authors.lastname: Hafezi
authors.forename: James M
authors.initials: JM
authors.lastname: Holcroft
authors.forename: Karel J
authors.initials: KJ
authors.lastname: Hartlieb
authors.forename: Edward J
authors.initials: EJ
authors.lastname: Dale
authors.forename: Nicolaas A
authors.initials: NA
authors.lastname: Vermeulen
authors.forename: Charlotte L
authors.initials: CL
authors.lastname: Stern
authors.forename: Amy A
authors.initials: AA
authors.lastname: Sarjeant
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
keywords: cage compounds; cyclophanes; host-guest complexes; supramolecular chemistry