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Published on: January 3, 2018
Interaction between f-electronic systems in dinuclear lanthanide complexes with phthalocyanines.
Naoto Ishikawa1, Tomochika Iino, Youkoh Kaizu
1Department of Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan. ishikawa@chem.titech.ac.jp
Journal of the American Chemical Society
|September 19, 2002
Summary
This study reveals ferromagnetic interactions in dinuclear lanthanide phthalocyanine complexes with f(8)-f(10) systems, and antiferromagnetic interactions in f(11) systems. These f-f interactions are primarily driven by magnetic dipolar terms.
Area of Science:
- Coordination Chemistry
- Magnetochemistry
- Lanthanide Chemistry
Background:
- Understanding interactions between f-electronic systems in dinuclear lanthanide complexes is crucial for developing novel magnetic materials.
- Phthalocyanine ligands offer a versatile platform for constructing such complexes with tunable electronic properties.
Purpose of the Study:
- To investigate and characterize the f-f interactions in dinuclear paramagnetic trivalent lanthanide complexes.
- To explore the relationship between the number of f-electrons and the nature of magnetic interactions (ferromagnetic vs. antiferromagnetic).
Main Methods:
- Synthesis of homodinuclear ([Ln, Ln]) and heterodinuclear ([Ln, Y]) lanthanide phthalocyanine complexes.
- Measurement of molar magnetic susceptibilities from 1.8 K to room temperature.
- Determination of ligand field parameters using magnetic susceptibility and 1H NMR data.
Main Results:
- Ferromagnetic f-f interactions were observed in [Tb, Tb], [Dy, Dy], and [Ho, Ho] complexes (f(8)-f(10)), with interaction strength increasing with f-electron count.
- Antiferromagnetic f-f interactions were found in [Er, Er] (f(11)) and [Tm, Tm] complexes.
- [Yb, Yb] complexes exhibited negligible f-f interactions.
Conclusions:
- The nature and strength of f-f interactions in these dinuclear lanthanide phthalocyanine complexes are strongly dependent on the number of f-electrons.
- Magnetic dipolar terms are identified as the primary contributors to the observed f-f interactions.
- This research provides fundamental insights into magnetic coupling in lanthanide-based molecular systems.
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