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Heptanuclear lanthanide [Ln7] clusters: from blue-emitting solution-stable complexes to hybrid clusters
Angelos B Canaj1, George K Tsikalas, Aggelos Philippidis
1Department of Chemistry, The University of Crete, Voutes, 71003, Herakleion, Greece. komil@chemistry.uoc.gr.
Dalton Transactions (Cambridge, England : 2003)
|May 14, 2014
Summary
Eight new lanthanide complexes were synthesized using LH3 and aibH ligands, exhibiting antiferromagnetic interactions and potential single-molecule magnetism. These novel clusters demonstrate structural integrity in solution and excellent thermal stability.
Area of Science:
- Coordination Chemistry
- 4f Chemistry
- Materials Science
Background:
- Lanthanide complexes are of interest for their unique magnetic and luminescent properties.
- Schiff base ligands and amino acids are versatile building blocks for constructing complex metal structures.
- Solvothermal synthesis offers a controlled environment for the formation of novel coordination compounds.
Purpose of the Study:
- To synthesize and characterize novel isostructural lanthanide complexes using LH3 and aibH.
- To investigate the magnetic properties, including exchange interactions and potential single-molecule magnetism.
- To explore the luminescent behavior and structural stability of the synthesized clusters.
Main Methods:
- Solvothermal synthesis reacting lanthanide nitrate salts with LH3 and aibH in methanol.
- Dc and ac magnetic susceptibility studies to probe magnetic interactions and dynamics.
- Solid-state emission spectroscopy and 1D/2D NMR studies for luminescence and structural integrity.
- Thermogravimetric analysis (TGA) for thermal stability assessment.
Main Results:
- Eight isostructural lanthanide clusters with the general formula [Ln(III)7(OH)2(L')9(aib)]·4MeOH were isolated.
- Dc susceptibility revealed dominant antiferromagnetic exchange interactions within the metallic clusters.
- The Dy(III)7 analogue exhibited temperature and frequency-dependent out-of-phase signals, indicating potential single-molecule magnetism.
- Ligand-based emission was observed in solid-state studies, and NMR confirmed structural integrity in solution.
- TGA showed excellent thermal stability up to 340 °C for selected complexes.
Conclusions:
- Novel isostructural lanthanide clusters were successfully synthesized and characterized.
- The complexes display interesting magnetic properties, including antiferromagnetic coupling and potential SMM behavior.
- The synthesized materials exhibit good thermal stability and retain their structure in solution, highlighting their potential for applications.
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