Yadav, Ravi and Maiti, Avijit and Schorpp, Marcel and Graf, Jürgen and Weigend, Florian and Greb, Lutz (2024) Supramolecular trapping of a cationic all-metal σ-aromatic {Bi4} ring. NATURE CHEMISTRY, 16 (9). pp. 1523-1530. ISSN 1755-4330, 1755-4349
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Aromaticity in organic molecules is well defined, but its role in metal-only rings remains controversial. Here we introduce a supramolecular stabilization approach of a cationic {Bi4} rhomboid within the symmetric charge sphere of two bowl-shaped dianionic calix[4]pyrrolato indinates. Crystallographic and spectroscopic characterization, quantum chemical analysis and magnetically induced ring currents indicate sigma-aromaticity in the formally tetracationic 16-valence electron [Bi-4](4+) ring. Computational screening for other p-block elements identifies the planar rhomboid as the globally preferred structure for 16-valence electron four-atomic clusters. The aromatic [Bi-4](4+) is isoelectronic to the [Al-4](4-), a motif previously observed as antiaromatic in Li-3[Al-4](-) in the gas phase. Thus, subtle factors such as charge isotropy seem to decide over aromaticity or antiaromaticity, advising for caution in debates based on the Huckel model-a concept valid for second-row elements but less deterministic for the heavier congeners.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | CRYSTAL-STRUCTURE; ORGANOMETALLIC COMPOUNDS; REDOX CHEMISTRY; ALKALI-METAL; CLUSTERS; ION; ANTIAROMATICITY; PORPHYRINOGEN |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 10 Dec 2025 06:09 |
| Last Modified: | 10 Dec 2025 06:09 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64747 |
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