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Emissive Ln(III)-Hg(II)/Pb(II) Coordination Polymers with Heteropolymeric 1-D Structures Synthesized
Thomas E Karpiuk1, Keqiang Yang1, Daniel B Leznoff1
1Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, British Columbia V5A 1S6, Canada.
Inorganic Chemistry
|May 22, 2025
Summary
Mechanochemical synthesis yielded novel heterobimetallic coordination polymers. These lanthanide-metal compounds exhibit unique 1-D structures and tunable photoluminescence properties, driven by anion exchange reactions.
Area of Science:
- Materials Chemistry
- Inorganic Chemistry
- Coordination Chemistry
Background:
- Lanthanide(III)-metal(II) coordination polymers offer diverse structural motifs and functional properties.
- Mechanochemical synthesis provides a solvent-free route for creating complex inorganic materials.
- Understanding structure-property relationships in heterobimetallic systems is crucial for materials design.
Purpose of the Study:
- To synthesize and characterize a new family of heterobimetallic lanthanide(III)-metal(II) coordination polymers using mechanochemistry.
- To investigate the structural diversity and formation mechanisms of these compounds, particularly focusing on anion-exchange reactions.
- To explore the photoluminescence properties of these materials, including energy transfer in mixed-lanthanide systems.
Main Methods:
- Mechanochemical synthesis involving anion-exchange reactions between lanthanide(III) bromide and metal(II) acetate salts.
- Single-crystal X-ray diffraction for structural elucidation of key compounds (e.g., EuHg, EuPb·DMF).
- Infrared (IR), Raman, and photoluminescence spectroscopy to characterize structural and optical properties.
Main Results:
- Successful synthesis of heterobimetallic coordination polymers [Ln(OAc)2(OH2)3](MBr3)]·xH2O (Ln=Eu, Tb, Eu/Tb; M=Hg, Pb).
- Crystal structure of EuHg revealed a 1-D heteropolymeric arrangement of cationic and anionic chains.
- Spectroscopic data indicated structural similarity between LnHg and LnPb compounds; EuPb·DMF exhibits a perovskite-like anionic chain.
Conclusions:
- Mechanochemical anion-exchange is an effective method for synthesizing novel heterobimetallic coordination polymers.
- The observed structures are driven by hard-soft acid-base interactions between metal ions and ligands.
- These materials display interesting photoluminescence characteristics, with potential for energy transfer applications in mixed-lanthanide systems.
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