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Developing a "highway code" to steer the structural and electronic properties of Fe(III)/Dy(III) coordination
Sihuai Chen1, Valeriu Mereacre1, Denis Prodius2,3
1†Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstrasse 15, 76131 Karlsruhe, Germany.
Inorganic Chemistry
|March 10, 2015
Summary
Ligand choice and reaction conditions control the topology of 3d/4f coordination clusters (CCs). Solvothermal conditions yield thermodynamically stable double-propeller structures, with one compound exhibiting single-molecule magnet behavior.
Area of Science:
- Coordination Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- The field of 3d/4f coordination cluster (CC) chemistry is emerging, presenting challenges in describing complex electronic structures and predicting favored core topologies.
- Combining transition metals (3d) and lanthanides (4f) in CCs offers potential for novel electronic properties.
Purpose of the Study:
- To investigate how the secondary coordination sphere, influenced by ligand choice, affects the formation of 3d/4f coordination clusters.
- To explore the impact of reaction conditions (ambient vs. solvothermal) on the resulting cluster structures.
- To determine the thermodynamic stability of different cluster topologies.
Main Methods:
- Synthesis of iron-dysprosium coordination clusters using varying benzoate ligands and reaction conditions.
- Structural characterization of the resulting coordination clusters.
- Investigation of electronic structures using magnetic and Mössbauer spectroscopy.
Main Results:
- Ligand substitution and reaction conditions dictate the formation of specific CC topologies, including 2Fe:2Dy:2Fe and "square-in-square" cores.
- Solvothermal treatment of initial products leads to thermodynamically stable "double-propeller" structures, irrespective of the initial ligand substitution.
- All synthesized compounds exhibit cooperative 3d/4f coupling, with one displaying single-molecule magnet behavior.
Conclusions:
- The secondary coordination sphere and reaction conditions are critical factors in controlling the self-assembly of 3d/4f coordination clusters.
- Solvothermal conditions favor the formation of thermodynamically stable "double-propeller" structures.
- The synthesized 3d/4f CCs represent promising systems for exploring cooperative magnetic phenomena and single-molecule magnet applications.
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