Unexpected Polymorphism in Bromoantimonate(III) Complexes and Its Effect on Optical Properties

Abstract

Reactions of [SbBr 6 ] 3− containing HBr solutions with bromide salts of 1,1′-(1,2-ethanediyl)bis(pyridine) (PyC 2 2+ ) or 1,1′-(1,2-ethanediyl)bis(3,5-dimethylpyridine) (3,5-MePyC 2 2+ ) initially result in the formation of the deep orange complexes Cat[SbBr 5 ] (1 and 2), featuring unusual Sb•••Br interactions in the solid state. In the mother liquor, 1 transforms into discrete binuclear (C 2 Py) 2 [Sb 2 Br 10 ], which demonstrates polymorphism (triclinic 3 and monoclinic 4), while 2 transforms into polymeric (3,5-MePy){[SbBr 4 ]} (5). DFT calculations reveal that the system of noncovalent Sb•••Br contacts may be responsible for the appearance of the observed optical properties (unusual deep orange coloring).

In situ recrystallization of zero-dimensional hybrid metal halide glass-ceramics toward improved scintillation performance

“…Besides organic cations, the physical and chemical properties of HMHs are dominantly determined by the inorganic anions in the crystal structure. 45,46 We attempted to broaden the synthetic pathway for HMH glasses to encompass various metal types of 0D HMH compounds through alterations of the inorganic anionic components. As an example, we selected an ionic liquid of ETPBr as the organic ligand to synthesize various metal ions containing 0D HMH, including Co 2+ , Ni 2+ , Zn 2+ and Bi 3+ with their corresponding crystal structures shown in ESI Fig.…”

Synthesis, Crystal, and Electronic Structure of (HpipeH2)2[Sb2I10](I2), with I2 Molecules Linking Sb2X10 Dimers into a Polymeric Anion: A Strategy for Optimizing a Hybrid Compound’s Band Gap

“…3− distorted octahedral anions and other simple anions with lower coordination numbers [22,23]. Octahedral anions can join into oligomers, with the number of Sb 3+ centers ranging from 2 to 10 [5, [24][25][26].…”

Halogen bonds regulating structures and optical properties of hybrid iodobismuthate perovskites

“…Factors known to influence the structures of hybrid halobismuthates include the choice of reagents, solvent system, and crystallization conditions (temperature, method, etc.). [20][21][22][23] Stoichiometry plays a crucial role in the synthesis of a specific halobismuthate. Nevertheless, due to simultaneously involving metal and halides in the anions, the products often violate the reagent (BiX 3 and the organic halide) stoichiometry used in the synthesis, particularly when the reaction is carried out in the presence of haloid acid.…”