Solvent-Induced Cluster-to-Cluster Transformation of Homoleptic Gold(I) Thiolates between Catenane and Ring-in-Ring Structures

Guang Tao Xu, Liang Liang Wu, Xiao Yong Chang, Tim Wai Hung Ang, Wai Yeung Wong, Jie Sheng Huang, Chi Ming Che

Research output: Journal article publicationJournal articleAcademic researchpeer-review

41 Citations (Scopus)

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 languageEnglish
Pages (from-to)16297-16306
Number of pages10
JournalAngewandte Chemie - International Edition
Volume58
Issue number45
DOIs
Publication statusPublished - 4 Nov 2019

Keywords

  • catenanes
  • gold
  • metallophilic interactions
  • supramolecular chemistry
  • thiolates

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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