Coordination site manipulation of the annular growth mechanism to assemble chiral lanthanide clusters with different shapes and magnetic properties

Abstract

Chiral lanthanide clusters provide a platform for molecular-based materials with coordination between chirality and magnetism, and exhibited great application prospects in the fields of three-dimensional displays, magneto-optical memories, and spintronic...

Homochiral Cu6Dy3 single-molecule magnets displaying proton conduction and a strong magneto-optical Faraday effect

“…41 Notably, although CH 2 Cl 2 is not present in the crystal lattices of R - 1 and S - 1 , it is essential for growing these homochiral Cu 3 Dy 6 cluster complexes’ single crystals, and when it is replaced with other solvents such as MeCN, the crystalline product cannot be obtained at all. Notably, although homochiral SMMs have been continuously exploited, 4–14,42–44 R - 1 and S - 1 are very rare homochiral Cu–Dy multinuclear cluster-type SMMs. Furthermore, a review of the latest CCDC database shows that R - 1 and S - 1 represent the first complexes assembled with the homochiral Schiff base ligands derived from 2-hydroxy-1-naphthalenecarboxaldehyde and (1 R ,2 R )/(1 S ,2 S )-2-aminocyclohexanol.…”

Highly stable drone-shaped lanthanide clusters: structure, assembly mechanism, and crystalline–amorphous transitions

“…26 Our research group has also made some progress in exploring the formation of high-nuclear lanthanide clusters. [29][30][31][32][33][34] For example, in 2019, we obtained Dy 10 nanoclusters with multiple relaxation behaviors by using Schiff base organic ligands having multidentate chelation coordination sites. After exploring their formation process, a step-bystep assembly mechanism was proposed by HRESI-MS. 29 We then constructed a cage-shaped cluster Dy 14 by connecting disc-shaped lanthanide clusters with strong hydrogen bonds and proposed its assembly mechanism.…”

“…31 Moreover, we proposed for the first time the out-to-in growth mechanism and the annular/linear growth mechanism of the self-assembly process of high-nuclear lanthanide clusters. 24,34 Overall, research on the formation process and assembly mechanism of high-nuclear lanthanide clusters is only beginning. Given that the intermediate fragments in the formation process are captured and screened, speculating on the formation process and assembly mechanism is important to explore the chemical reaction nature and elementary reactions of high-nuclear lanthanide clusters.…”

Double butterfly-shaped octanuclear dysprosium clusters: structure, magnetism and assembly mechanism

“…Although it is difficult to track the self-assembly process of lanthanide clusters and study the assembly mechanism, our research group has made a series of advances in this field in recent years. 19,23,24,32,38–41 For example, in 2018, we used N -methylbenzimidazole-2-methanol and Dy(NO 3 ) 3 ·6H 2 O to synthesize a triangular trinuclear dysprosium cluster (Dy 3 ) with single-molecule toroic magnetic moment under solvothermal conditions at 80 °C, and its progressive fragmentation process was tracked using HRESI-MS. Furthermore, the assembly process of Dy 3 was followed by time-dependent HRESI-MS and its assembly mechanism was deduced.…”

“…Structural analysis shows that the cluster R / S - 1 is a tetranuclear square chiral cluster assembled by 8 R / S -HL 1 ligand molecules and 4 Dy( iii ) ions; cluster R / S - 2 is a hexanuclear triangular pyramidal cluster assembled by 3 R / S -HL 2 ligand molecules and 6 Dy( iii ) ions. 41 Therefore, it is very important to capture and identify the intermediates in the formation process of lanthanide clusters, and then track and analyze their assembly mechanism for the directional design and synthesis of lanthanide clusters with special structural connections and excellent magnetic properties.…”