“…To investigate the nature of Br⋅⋅⋅Br interactions in all new compounds, as well as in the already known Sb V polybromides, we carried out DFT calculations and performed topological analysis of the electron density distribution within the framework of Bader's theory (QTAIM method) for corresponding model supramolecular clusters (obtained from XRD data) featuring Br⋅⋅⋅Br contacts shorter than the sum of Bondi's van der Waals radii . This approach has already been used in our studies of different non‐covalent interactions, for example, hydrogen, halogen, and chalcogen bonding, stacking, as well as metallophilic interactions . The results are summarized in Table S1 (in the Supporting Information; the contour line diagrams of the Laplacian distribution ▿ 2 ρ ( r ), bond paths, and selected zero‐flux surfaces for 3 and 4 are shown in Figures and .…”