Halogen bonding-assisted assembly of bromoantimonate(v) and polybromide-bromoantimonate-based frameworks

Abstract

Halogen bonding within bromo- and polybromoantimonates(v).

Antimony(V) Bromide and Polybromide Complexes with N‐alkylated Quinolinium or Isoquinolinium Cations: Substituent‐dependent Assembly of Polymeric Frameworks

“…Interestingly, the energies of the interactions in pairs of bromide ligands of [Sb V Br 6 ] – are greater than those of Br term ··· Br Br3 (1.3–1.8 vs. 1.6–2.1 kcal · mol –1 ). This observation agrees well with the results reported by us earlier;, most likely, these interactions in bromidoantimonates(V) are responsible for enhanced photophysical response encountered in N‐ethylpyridinium salt of [Sb V Br 6 ] – …”

“…These results agree with the data obtained for other related complexes:, thermal decmoposition of Cat[Sb V Br 6 ] salts is rather trivial, while behavior of polybromide‐bromidoantimonates(V) is generally sophisticated, and interpretation of TGA results is usually challenging.…”

“…In the case of 1 and 2 , the anionic parts have the same brutto formulae (“SbBr 9 ”). According to our statistics, this composition is one of the most frequently encountered in polybromide‐bromidoantimonates. However, the molecular structures of “SbBr 9 ” complexes can be different.…”

“…The anionic part of 3 consists only of [Sb V Br 6 ] – anions. This structural type is relatively common; however, the system of Br ··· Br interactions in solid state can be different, resulting in one‐, two‐ or three‐dimensional structures. In the case of 3 , all such distances are equal (3.505 Å) and there form 2D layers (Figure ).…”

“…Earlier we published a series of bromo‐ and polybromoantimonate(V) complexes containing up to 11 bromine atoms per one Sb, prepared using various substituted pyridinium cations. We reported their thermal stability and insights into the nature of Br ··· Br interactions , . Hereby we introduce three novel complexes of this series prepared using N‐substituted quinolinium and isoquinolinium derivatives, (N‐MeQuin){[SbBr 6 ](Br 3 )} ( 1 ), (N‐MeIsoquin){[SbBr 6 ](Br 3 )}, ( 2 ) and (N‐EtQuin)[SbBr 6 ] ( 3 ), their structure and thermal stability, as well as estimation of Br ··· Br interaction energies.…”