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Framework engineering by anions and porous functionalities of Cu(II)/4,4'-bpy coordination polymers
Shin-ichiro Noro1, Ryo Kitaura, Mitsuru Kondo
1Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Journal of the American Chemical Society
|March 14, 2002
Summary
Novel porous coordination polymers were synthesized using copper(II) ions, 4,4′-bipyridine ligands, and various anions. These materials exhibit tunable structures and dynamic anion-exchange properties, demonstrating framework control by counteranions.
Area of Science:
- Materials Science
- Inorganic Chemistry
- Supramolecular Chemistry
Background:
- Porous coordination polymers (PCPs) offer tunable structures for various applications.
- Controlling the framework and properties of PCPs through rational design is a key challenge.
- Anions play a crucial role in directing the assembly and stability of coordination networks.
Purpose of the Study:
- To synthesize and characterize novel porous coordination polymers using a combination of Cu(II) ions, 4,4'-bipyridine, and different framework-regulating anions.
- To investigate the structural diversity and dynamic behavior of these materials in response to varying anionic components.
- To explore the influence of counteranions on the formation and interconversion of PCP frameworks.
Main Methods:
- Solvothermal synthesis of coordination polymers.
- Single-crystal X-ray diffraction for structural elucidation.
- Powder X-ray diffraction and thermogravimetric analysis for characterization.
- In-situ conversion studies to observe framework transformations.
Main Results:
- A series of novel 3-D and 2-D porous coordination polymers were successfully synthesized.
- Frameworks ranged from robust 3-D microporous networks to interpenetrated 2-D structures.
- Structural conversions were observed upon water immersion or by altering the counteranions (e.g., AF(6)(2-) to PF(6)(-)).
- Dynamic anion-exchange properties and selective framework transformations were demonstrated, highlighting anion-templated assembly.
Conclusions:
- The rational selection of framework-builder and framework-regulator components allows for the controlled synthesis of diverse PCP architectures.
- Anions significantly influence the dimensionality, interpenetration, and dynamic properties of Cu(II)-based coordination polymers.
- These findings provide insights into the design principles for creating functional porous materials with tunable properties.
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