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Solvent‐Induced Cluster‐to‐Cluster Transformation of Homoleptic Gold(I) Thiolates between Catenane and Ring‐in‐Ring Structures
Author(s) -
Xu GuangTao,
Wu LiangLiang,
Chang XiaoYong,
Ang Tim Wai Hung,
Wong WaiYeung,
Huang JieSheng,
Che ChiMing
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201909980
Subject(s) - catenane , homoleptic , ring (chemistry) , cluster (spacecraft) , chemistry , transformation (genetics) , crystallography , stereochemistry , organic chemistry , metal , computer science , molecule , biochemistry , programming language , gene
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 d 10 –d 10 Au I –Au I 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 Au I ‐thiolate Au 12 cluster formed by recrystallization of a Au I ‐thiolate Au 10 [2]catenane from alkane solvents such as hexane, with use of a bulky dibutylfluorene‐2‐thiolate ligand. The ring‐in‐ring Au I ‐thiolate Au 12 cluster features inter‐ring Au I –Au I interactions and underwent cluster core change to form the thermodynamically more stable Au 10 [2]catenane structure upon dissolving in, or recrystallization from, other solvents such as CH 2 Cl 2 , CHCl 3 , and CH 2 Cl 2 /MeCN. The cluster‐to‐cluster transformation process was monitored by 1 H 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.