Theoretical investigation of tube-like supramolecular structures formed through bifurcated lithium bonds

Forough Rezaie; Siamak Noorizadeh

doi:10.1038/s41598-023-41979-5

Theoretical investigation of tube-like supramolecular structures formed through bifurcated lithium bonds

Sci Rep. 2023 Sep 14;13(1):15260. doi: 10.1038/s41598-023-41979-5.

Authors

Forough Rezaie¹, Siamak Noorizadeh²

Affiliations

¹ Chemistry Department, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz, Iran.
² Chemistry Department, Faculty of Sciences, Shahid Chamran University of Ahvaz, Ahvaz, Iran. noorizadeh_s@scu.ac.ir.

Abstract

The stability of three supramolecular naostructures, which are formed through the aggregation of identical belts of [12] arene containing p-nitrophenyllithium, 1,4-dilithiatedbenzene and 1,4-dinitrobenzene units, is investigated by density functional theory. The electrostatic potential calculations indicate the ability of these belts in forming bifurcated lithium bonds (BLBs) between the Li atoms of one belt and the oxygen atoms of the NO₂ groups in the other belt, which is also confirmed by deformation density maps and quantum theory of atoms in molecules (QTAIM) analysis. Topological analysis and natural bond analysis (NBO) imply to ionic character for these BLBs with binding energies up to approximately - 60 kcal mol^-1. The many-body interaction energy analysis shows the strong cooperativity belongs to the configuration with the highest symmetry (C_4v) containing p-nitrophenyllithium fragments as the building unit. Therefore, it seems that this configuration could be a good candidate for designing a BLB-based supramolecular nanotube with infinite size in this study.