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 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 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⇌ catenane” interconversions.
|Number of pages||10|
|Journal||Angewandte Chemie - International Edition|
|Publication status||Published - 4 Nov 2019|
- metallophilic interactions
- supramolecular chemistry
ASJC Scopus subject areas