Assembly of Dy60 and Dy30 cage-shaped nanoclusters
Zhi-Rong Luo, Hai‐Ling Wang, Zhong‐Hong Zhu, Tong Liu, Xiongfeng Ma, Huifeng Wang, Hua‐Hong Zou, Fu‐Pei Liang
Abstract
Abstract Rapid kinetics, complex and diverse reaction intermediates, and difficult screening make the study of assembly mechanisms of high-nuclearity lanthanide clusters challenging. Here, we synthesize a double-cage dysprosium cluster [Dy 60 (H 2 L 1 ) 24 (OAc) 71 (O) 5 (OH) 3 (H 2 O) 27 ]·6H 2 O·6CH 3 OH·7CH 3 CN ( Dy 60 ) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy 30 cages are included in the Dy 60 structure, which are connected via an OAc − moiety. The core of Dy 60 is composed of 8 triangular Dy 3 and 12-fold linear Dy 3 units. We further change the alkali added in the reaction system and successfully obtain a single cage-shaped cluster [Dy 30 (H 2 L 1 ) 12 (OAc) 36 (OH) 4 (H 2 O) 12 ]·2OH·10H 2 O·12CH 3 OH·13CH 3 CN ( Dy 30 ) with a perfect spherical cavity, which could be considered an intermediate in Dy 60 formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy 60 . A possible self-assembly mechanism is proposed. We track the formation of Dy 30 and the six intermediate fragments are screened.