Yu Shui, Hu Huancheng, Zou Hua-Hong, Liu Dongcheng, Liang Yuning, Liang Fu-Pei, Chen Zilu
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, People's Republic of China.
Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541004, People's Republic of China.
Inorg Chem. 2022 Feb 28;61(8):3655-3663. doi: 10.1021/acs.inorgchem.1c03768. Epub 2022 Feb 15.
A full understanding of the assembly mechanisms of coordination complexes is of great importance for a directional synthesis under control. We thus explored here the formation mechanisms of the two new heterometallic nanoclusters [DyNi(μ-OH)(L)(OAc)(HO)]·3.25EtOH·4CHCN () and [DyMnMnO(OH)(OAc)(L)(HL)(EtOH)]·2EtOH·2CHCN·2HO () with different cubane-based squarelike ring structures, which were obtained from the reactions of 4-bromo-2-[(2-hydroxypropylimino)methyl]phenol (HL) with Dy(NO)·6HO and the transition metal salt Ni(OAc)·4HO or Mn(OAc)·4HO. The high-resolution electrospray ionization mass spectrometry (HRESI-MS) tests showed that the skeletons of clusters and have a high stability under the measurement conditions for HRESI-MS. The intermediates formed in the reaction courses of clusters and were tracked using time-dependent HRESI-MS, which helped to determine the proposed hierarchical assembly mechanisms for (HL → NiL → NiL → NiL → NiL → DyNiL → DyNiL → DyNiL → DyNiL → DyNiL) and (HL → MnL → DyMnL → DyMnL → DyMnL → DyMnL → DyMnL → DyMnL and HL → DyL → DyL → DyL → DyMnL → DyMnL → DyMnL). This is one of the rare examples of investigating the assembly mechanisms of 3d-4f heterometallic clusters. Magnetic studies indicated that the title complexes both show slow magnetic relaxation behaviors and cluster is a field-induced single-molecule magnet.
