Issue 5, 2022

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 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.

Graphical abstract: Janusene as a silver ion scavenger: insights from computation

Supplementary files

Article information

Article type
Paper
Submitted
09 Aug 2021
Accepted
05 Dec 2021
First published
07 Dec 2021

New J. Chem., 2022,46, 2393-2404

Janusene as a silver ion scavenger: insights from computation

M. C. Colaço, G. F. Caramori, R. L. T. Parreira and K. K. Laali, New J. Chem., 2022, 46, 2393 DOI: 10.1039/D1NJ03833H

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