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Journal Article

The Mixed-Valence Catena-Heteropolycation (Bi2S2)+


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

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Knies, M., Nawroth, P., Golub, P., Isaeva, A., & Ruck, M. (2021). The Mixed-Valence Catena-Heteropolycation (Bi2S2)+. Zeitschrift für anorganische und allgemeine Chemie, 1-6. doi:10.1002/zaac.202100188.

Cite as: http://hdl.handle.net/21.11116/0000-0009-42AB-C
The reaction of Bi and Bi2S3 in the Lewis-acidic ionic liquid [BMIm]Cl . 4.3AlCl(3) (BMIm=1-n-butyl-3-methylimidazolium) at 200 degrees C yielded air-sensitive black crystals of (Bi2S2)[AlCl4]. X-ray diffraction on single-crystals revealed a monoclinic structure containing infinite chains infinity 1(Bi2S2) + . These polycations contain bismuth(II,III) and sulfur(-II) atoms, connected by polar covalent Bi-S and Bi-Bi bonds. The assignment of bonds is ambiguous as a distinction between primary and secondary interactions is arbitrary based on interatomic distances. A real-space quantum chemical bonding analysis, including delocalization indices, helped to quantify the interactions and charge distribution, confirming that a simple Lewis formula is inappropriate to describe the polycation.