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 [Dy60(H2L1)24(OAc)71(O)5(OH)3(H2O)27]·6H2O·6CH3OH·7CH3CN (Dy60) by using a multidentate chelate-coordinated diacylhydrazone ligand. Two Dy30 cages are included in the Dy60 structure, which are connected via an OAc− moiety. The core of Dy60 is composed of 8 triangular Dy3 and 12-fold linear Dy3 units. We further change the alkali added in the reaction system and successfully obtain a single cage-shaped cluster [Dy30(H2L1)12(OAc)36(OH)4(H2O)12]·2OH·10H2O·12CH3OH·13CH3CN (Dy30) with a perfect spherical cavity, which could be considered an intermediate in Dy60 formation. Time-dependent, high-resolution electrospray ionization mass spectrometry (HRESI-MS) is used to track the formation of Dy60. A possible self-assembly mechanism is proposed. We track the formation of Dy30 and the six intermediate fragments are screened.

High-nuclearity lanthanide clusters can exhibit interesting properties such as magnetism, but the mechanisms by which they assemble are poorly understood. Here, the formation of two dysprosium nanoclusters containing 30 or 60 atoms is followed over time by mass spectrometry and proposed to follow a seven-step assembly mechanism.

Details

Title
Assembly of Dy60 and Dy30 cage-shaped nanoclusters
Author
Zhi-Rong, Luo 1 ; Hai-Ling, Wang 1 ; Zhong-Hong, Zhu 1   VIAFID ORCID Logo  ; Liu, Tong 1 ; Xiong-Feng, Ma 1 ; Hui-Feng, Wang 1 ; Hua-Hong, Zou 1 ; Fu-Pei, Liang 2 

1  School of Chemistry and Pharmacy of Guangxi Normal University, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guilin, China (GRID:grid.459584.1) (ISNI:0000 0001 2196 0260) 
2  School of Chemistry and Pharmacy of Guangxi Normal University, State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Guilin, China (GRID:grid.459584.1) (ISNI:0000 0001 2196 0260); Guilin University of Technology, Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin, China (GRID:grid.440725.0) (ISNI:0000 0000 9050 0527) 
Publication year
2020
Publication date
2020
Publisher
Nature Publishing Group
e-ISSN
23993669
Source type
Scholarly Journal
Language of publication
English
DOI
https://doi.org/10.1038/s42004-020-0276-3
ProQuest document ID
2376714074
Copyright
This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.