Solvent-Induced Cluster-to-Cluster Transformation of Homoleptic Gold(I) Thiolates between Catenane and Ring-in-Ring Structures.
Angew Chem Int Ed Engl
; 58(45): 16297-16306, 2019 Nov 04.
Article
em En
| MEDLINE
| ID: mdl-31486262
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 CH2 Cl2 , CHCl3 , and CH2 Cl2 /MeCN. The cluster-to-cluster transformation process was monitored by 1 Hâ
NMR and ESI-MS measurements. Density functional theory (DFT) calculations were performed to provide insight into the mechanism of the "ring-in-ringâ [2]catenane" interconversions.
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MEDLINE
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En
Ano de publicação:
2019
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Article