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Assembly of pinwheel/twist-shaped chiral lanthanide clusters with rotor structures by an annular/linear growth mechanism and their magnetic properties.
- Source :
-
Dalton Transactions: An International Journal of Inorganic Chemistry . 11/28/2022, Vol. 51 Issue 44, p17040-17049. 10p. - Publication Year :
- 2022
-
Abstract
- Although progress has been made in the design and synthesis of chiral lanthanide clusters with pleasing structural connections and special shapes, assembly rules that guide their directional construction are still lacking. We reacted R/S -mandelic acid hydrazide, 2,3-dihydroxybenzaldehyde and DyCl3·6H2O under solvothermal conditions to obtain two octanuclear chirality clusters R-1 and S-1 , which are the enantiomers of each other. R/S -mandelic acid hydrazide and 2,3-dihydroxybenzaldehyde underwent an in situ reaction under "one-pot" conditions to generate a monohydrazone-type organic ligand R/S -mandelic acid hydrazide-2,3-dihydroxybenzaldehyde hydrazone (R/S -H2L). Four R/S -H2L ligands captured eight metal-centered Dy(III) ions and presented an annular arrangement, which assembled to form a pinwheel-shaped chiral cluster R/S-1. The benzene rings at the four vertices of R/S-1 can rotate freely as rotors. This is the first discovery of an annular growth mechanism during the self-assembly of lanthanide clusters. By changing the metal salt to Dy(NO3)3·6H2O, two twist-shaped hexanuclear clusters R-2 and S-2 , which are the enantiomers of each other were obtained. Four R/S -H2L and two R/S -H3L ligands captured six metal-centered Dy(III) ions, respectively, and were assembled through a linear growth mechanism to form the twist-shaped chiral clusters R/S-2. This is the first time that a linear growth mechanism has been proposed for the directional construction of lanthanide clusters with specific shapes. Circular dichroism results showed that R/S-1 and R/S-2 were both chiral clusters and enantiomers of each other. Magnetic studies showed that both R/S-1 and R/S-2 exhibit obvious single-molecule magnet (SMM) behaviors under zero-field conditions. This work is the first to propose an annular/linear growth mechanism for the design and synthesis of lanthanide clusters and allows the directional construction of chiral lanthanide clusters with special shapes and structural connections. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 51
- Issue :
- 44
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 160236154
- Full Text :
- https://doi.org/10.1039/d2dt02653h