Janusene as a silver ion scavenger: insights from computation

Abstract

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...

Supramolecular Chemistry: Exploring the Use of Electronic Structure, Molecular Dynamics, and Machine Learning Approaches

“…The ability of janusene, a [3,3]ortho‐cyclophane, to stabilize Ag + ion was verified by canonical energy decomposition analysis in conjunction with the ETS‐NOCV, alongside topological analysis of electron density (QTAIM). The initial results show the capacity to coordinate multiple silver cations, up to five Ag + simultaneously, where thirty‐five converged structures as local minima were identified [41] . The molecular electrostatic potential (MEP) reveals that different coordination positions of silver ions modify the electron density of janusene, thereby influencing its reactivity and the nature of interactions (Figure 7).…”

“…The initial results show the capacity to coordinate multiple silver cations, up to five Ag + simultaneously, where thirty-five converged structures as local minima were identified. [41] The molecular electrostatic potential (MEP) reveals that different coordination positions of silver ions modify the electron density of janusene, thereby influencing its reactivity and the nature of interactions (Figure 7). This modification in the electron density of janusene rings activates them towards electrophilic aromatic substitution and nucleophilic aromatic substitution, depending on the coordination position of Ag + in relation to janusene.…”

How Do Face-to-Face Stacked Aromatic Rings Activate Each Other to Electrophilic Aromatic Substitution?

“…As the aromatic rings approach one another face-to-face, HOMO energy increases, which theoretically makes the array more reactive to an electrophile. The literature reveals some indication that face-to-face stacked aromatic rings can influence each other in select EAS reactions . For example, the molecule janusene (Scheme ) was shown to undergo preferential nitration at the stacked ring, although very precise structural assignments were lacking at the time of publication.…”