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Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids

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Ruck,  Michael
Michael Ruck, Max Planck Fellow, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Knies, M., & Ruck, M. (2021). Salts of octabismuth(2+) polycations crystallized from Lewis-acidic ionic liquids. Zeitschrift für Naturforschung, B: A Journal of Chemical Sciences, 1-5. doi:10.1515/znb-2021-0042.


Cite as: http://hdl.handle.net/21.11116/0000-0008-E980-0
Abstract
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 ABX3 with A = (Bi8)2+, B = M+ and X = [AlCl4]-. Chiral strands ∞{M[AlCl4]3}2- (M = Rb, Cs) run along [001]. 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. © 2021 Walter de Gruyter GmbH, Berlin/Boston 2021.