Janusene as a silver ion scavenger: insights from computation

Janusene is a [3,3] ortho -cyclophane that possesses four aromatic moieties of which two are held together in a quasi-parallel or in a cleft-shaped arrangement. The multiple coordination sites available in janusene were tested by bonding of Ag + ions in different positions of the janusene structure, leading to 35 systems. Our results evidence that janusene is able to stabilize up to five Ag + ions simultaneously. Due to the symmetric coordination positions, several isomers have been obtained with systems containing up to 4 Ag + ions. Janusene-Ag + interactions, for all systems, are partially covalent in nature, mainly stabilized by Δ E orb and Δ E ele interactions. MEP isosurfaces reveal that the different Ag + coordination modifies the janusene electron density, thus modulating the reactivity of its rings. Janusene is also able to stabilize, by −130 kcal mol −1 , a [Ag A Ag B ] 2+ interaction at short distances, in the cleft between facial rings. Interestingly, these interactions are enhanced by coordination of other Ag + ions, increasing the lateral rings' orbital interactions to the stabilization of the [Ag A Ag B ] 2+ interaction. This study reveals the presence of some unusual and previously unexplored features of janusene's electronic structure. The ability of Janusene to interact simultaneously with multiple silver ions.