Chlorobismuthates Trapping Dibromine: Formation of Two‐Dimensional Supramolecular Polyhalide Networks with Br₂ Linkers

Abstract

Reactions between BiCl3, Br2, and chlorides of pyridinium (1), 4,4′‐propylenedipyridinium (2), or trimethylphenylammonium (3) in aqueous HCl lead to the formation of chlorobismuthate complexes trapping {Br2} in the solid state into two‐dimensional polyhalide supramolecular networks. The nature of non‐covalent Br···Cl interactions was studied by theoretical methods; estimated energies of these interactions are 1.9–6.0 kcal/mol.

Rule, Not Exclusion: Formation of Dichlorine-Containing Supramolecular Complexes with Chlorometalates(IV)

“…Previously, we have noticed a clear tendency of di- or polyhalogens to form specific supramolecular hybrids with anionic halide complexes (halometalates) in the solid state. The formation of halogen bonding (XB) enables “trapping” of polyhalides in a crystalline state, so that halogen-rich complexes can be prepared, sometimes unexpectedly easily. − This feature is especially common for halometalates of groups 15 and 16: in our work, we succeeded in the isolation of polybromo bromometalates (M = Bi­(III), , Te­(IV), Sb­(V)), polybromo chlorometalates (M = Bi­(III), Te­(IV)), etc. of remarkable structural diversity.…”

Opening the Third Century of Polyhalide Chemistry: Thermally Stable Complex with “Trapped” Dichlorine

“…In these, di‐ or polyhalogen units are connected with halometalates via non‐covalent halogen⋅⋅⋅halogen interactions (in the solid), forming supramolecular assemblies of diverse architectures. Systematically pursuing this rather straightforward approach, we successfully prepared novel polybromide‐bromobismuthates(III) [17, 18] and ‐chlorobismuthates(III), [19] polybromide‐bromotellurates [20] etc. In some cases, this method permits “capture” of unusual polyhalide species such as T‐shaped planar {Br 9 } 4− [21] .…”

Noncovalent Bonds, Spectral and Thermal Properties of Substituted Thiazolo[2,3-b][1,3]thiazinium Triiodides

“…Variation of the N-and S-containing heterocyclic cations is useful for the investigation of bonding properties in organic polyiodide crystals. The chemistry of polyhalides has attracted particular attention due to the vast diversity of applicable properties related to the ability of halogens to form different types of contacts [10][11][12][13][14][15]. Polyiodides represent an absolute majority among polyhalide structures [16][17][18][19][20][21].…”