Role of I₂ Molecules and Weak Interactions in Supramolecular Assembling of Pseudo-Three-Dimensional Hybrid Bismuth Polyiodides: Synthesis, Structure, and Optical Properties of Phenylenediammonium Polyiodobismuthate(III)

Abstract

Phenylenediammonium polyiodobismuthate­(III), [PDA­(BiI4)2·​I2] (PDA = phenyl­ene­diam­monium, [NH3­C6H4­NH3]2+), represents a new hybrid halometallate synthesized in a form of black well-shaped crystals by a facile reaction in aqueous solution of HI containing dissolved I2. It crystallizes in triclinic space group P1̅ with the unit cell parameters a = 7.761(1) Å, b = 9.259(1) Å, c = 9.689(1) Å, α = 95.68(3)°, β = 103.19(3)°, γ = 93.56(3)°, and Z = 1. Its crystal structure comprises three levels of organization discriminated by a type of chemical bonding. The first level is provided by covalently bonded [BiI6] octahedra linked into [BiI4]∞ – one-dimensional anionic chains; the second level features secondary bonds between the chains and I2 bridging molecules, whereas the third level is specified by the weak hydrogen N–H···I bonds involving a diammonium cation and I···I intermolecular interactions that additionally link anionic chains. Altogether, these three interaction types ensure the formation of a complex pseudo-three-dimensional crystal structure. According to optical absorption study, [PDA­(BiI4)2·​I2] is a semiconductor with the band gap of 1.45 eV.

1D and 2D Polybromotellurates(IV): Structural Studies and Thermal Stability

“…We have shown that formation of polyhalide/bromotellurate hybrids in a simple “cationBr x + Br 2 + HBr + [TeBr 6 ] 2– ” system is not uncommon, and in the case of tri‐ or tetraalkylammonium cations forming, the products reveal remarkable stability (unlike the family of complexes containing pyridinium‐type cations reported earlier). This observation may be important in the course of designing other polyhalide/halometalate hybrids which are of particular interest for photovoltaic applications . From the structural point of view, it can be seen that, although bromotellurates(V) preferably form mononuclear species, the diversity of supramolecular patterns based on Br ··· Br interactions may be richer than it would be expected by looking at the additional contacts.…”

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

“…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]. The interest in polyiodide derivatives is based on their enormous structural diversity of packing motives resulting in the formation of anionic ribbons, layers, channels and sheets [22][23][24].…”

A Novel Family of Polyiodo‐Bromoantimonate(III) Complexes: Cation‐Driven Self‐Assembly of Photoconductive Metal‐Polyhalide Frameworks

“…The most recent advances were achieved in the area of non-iodide polyhalides, for example, synthesis and theoretical studies of enhancedp olybromide frameworks [4][5][6] andp olychlorides; [7] the latter are of special interest due to the clearly decreasing ability to form polyhalides in the I > Br > Cl @ Fr ow.H owever,d espite the generalp rogress in this field, it can be noted that the polyhalide metal complexes remaini ncomparably lesse xplored. For the all-polyhalidec omplexes, single examplesa re known for polyiodides [8][9][10][11] and polybromides. [12][13][14][15][16][17] Coordination of mixed polyhalides( (BrI 2 ) À , (ClBr 2 ) À )w as reported mostly for heteroligand complexes.…”