Abstract
Supramolecular ensembles adopting ring-in-ring structures are less developed compared with catenanes featuring interlocked rings. While catenanes with inter-ring closed-shell metallophilic interactions, such as d10–d10 AuI–AuI interactions, have been well-documented, the ring-in-ring complexes featuring such metallophilic interactions remain underdeveloped. Herein is described an unprecedented ring-in-ring structure of a AuI-thiolate Au12 cluster formed by recrystallization of a AuI-thiolate Au10 [2]catenane from alkane solvents such as hexane, with use of a bulky dibutylfluorene-2-thiolate ligand. The ring-in-ring AuI-thiolate Au12 cluster features inter-ring AuI–AuI interactions and underwent cluster core change to form the thermodynamically more stable Au10 [2]catenane structure upon dissolving in, or recrystallization from, other solvents such as CH2Cl2, CHCl3, and CH2Cl2/MeCN. The cluster-to-cluster transformation process was monitored by 1H NMR and ESI-MS measurements. Density functional theory (DFT) calculations were performed to provide insight into the mechanism of the “ring-in-ring⇌ [2]catenane” interconversions.
Original language | English |
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Pages (from-to) | 16297-16306 |
Number of pages | 10 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 45 |
DOIs | |
Publication status | Published - 4 Nov 2019 |
Keywords
- catenanes
- gold
- metallophilic interactions
- supramolecular chemistry
- thiolates
ASJC Scopus subject areas
- Catalysis
- General Chemistry