The reaction of Bi and BiCl3 with RbCl or CsCl in the Lewis-acidic ionic liquid (IL) [BMIm]Cl·4AlCl3 at T = 200 °C yielded air-sensitive, shiny black crystals. X-ray diffraction on single crystals revealed the hexagonal structures of two new salts (Bi8)M[AlCl4]3 (M = Rb, Cs), which are isostructural to the high-temperature form of (Bi8)Tl[AlCl4]3. The known (Bi8)2+ polycation is a square antiprism and can be interpreted as an arachno cluster following modified Wade rules. The crystal structure is a complex variant of the hexagonal perovskite structure type ABX 3 with A = (Bi8)2+, B = M + and X = [AlCl4]–. Chiral strands (M = Rb, Cs) run along . The (Bi8)2+ polycations are only weakly coordinated inside a cage of 24 chloride ions and show dynamic rotational disorder at room temperature. Upon slow cooling to 170 K, the reorientation of the clusters was frozen, yet no long-range order was established.
Funding source: Deutsche Forschungsgemeinschaft
We acknowledge technical support by M. Münch and A. Brünner (TU Dresden).
Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This research was funded by the Deutsche Forschungsgemeinschaft (DFG) within the Priority Program SPP 1708.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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