Janusene as a silver ion scavenger: Insights from computation

Document Type

Article

Publication Date

2-7-2022

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 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 ΔEorb and ΔEele 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 [AgA⋯AgB]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 [AgA⋯AgB]2+ interaction. This study reveals the presence of some unusual and previously unexplored features of janusene's electronic structure. This journal is

Publication Title

New Journal of Chemistry

Volume

46

Issue

5

First Page

2393

Last Page

2404

Digital Object Identifier (DOI)

10.1039/d1nj03833h

ISSN

11440546

E-ISSN

13699261

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