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Chiral Erbium(III) Complexes: Single-Molecule Magnet Behavior, Chirality, and Nuclearity Control
Min Feng1, Bang-Heng Lyu1, Ming-Hui Wang1
1Key Laboratory of Bioinorganic and Synthetic Chemistry of the Ministry of Education, School of Chemistry , Sun Yat-Sen University , Guangzhou 510275 , P. R. China.
Inorganic Chemistry
|August 8, 2019
Summary
Chiral erbium phosphate complexes with controllable nuclearity were synthesized. These enantiomers exhibit unique magnetic relaxation properties, explained by ab initio calculations and ferromagnetic interactions.
Area of Science:
- Coordination Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- Chiral ligands are crucial for developing novel coordination complexes with specific properties.
- Lanthanide complexes, particularly erbium, are of interest for their magnetic and optical characteristics.
- Controlling nuclearity in metal complexes can lead to unique structures and functionalities.
Purpose of the Study:
- To synthesize and characterize di- and tetranuclear chiral erbium phosphate complexes.
- To investigate the influence of reaction temperature on complex nuclearity.
- To explore the magnetic properties and relaxation pathways of the synthesized erbium complexes.
Main Methods:
- Reaction of chiral 1,1'-binaphthyl-2,2'-diyl phosphate ligand with ErCl3·6H2O.
- Crystallization and structural characterization of di- and tetranuclear erbium complexes.
- Circular dichroism (CD) spectroscopy to confirm chirality.
- Magnetic measurements and ab initio calculations to study magnetic relaxation.
Main Results:
- Two pairs of di- and tetranuclear erbium enantiomers, [Er2(L)4(EtOH)6]Cl2 (1) and [Er4(PO4)(L)8(EtOH)3(H2O)]2Cl(OH) (2), were successfully synthesized.
- Complex nuclearity was found to be controllable by reaction temperature, influenced by a template effect.
- Circular dichroism spectra confirmed the chirality of the synthesized complexes.
- Complex R-1 displayed two magnetic relaxation pathways with a 40 K energy barrier, attributed to ferromagnetic dipolar interactions and equatorial ligand fields.
Conclusions:
- The study demonstrates the successful synthesis of chiral di- and tetranuclear erbium phosphate complexes with temperature-controlled nuclearity.
- The chirality and magnetic properties of these complexes were thoroughly investigated.
- Ab initio calculations provide insights into the magnetic relaxation mechanisms in these erbium complexes.
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