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Functional tetrametallic linker modules for coordination polymers and metal-organic frameworks.
Frank B Johansson1, Andrew D Bond, Christine J McKenzie
1Department of Physics and Chemistry, University of Southern Denmark, Campusvej 55, 5230 Odense M, Denmark.
Inorganic Chemistry
|February 24, 2007
Summary
This study introduces a novel tetranucleating ligand, dbpbp2-, for creating metal complexes. These complexes, including cobalt-dioxygen adducts, show potential for constructing coordination polymers and metal-organic frameworks with reversible O2 binding capabilities.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Development of multimetallic complexes with novel ligands is crucial for advanced materials.
- Tetranucleating ligands offer unique coordination environments for metal ions.
- Understanding metal-ligand interactions is key to designing functional coordination compounds.
Purpose of the Study:
- To synthesize and characterize a new biphenol-based tetranucleating ligand (dbpbp2-).
- To explore the coordination chemistry of this ligand with various transition metal ions (ZnII, CuII, FeIII, CoII/III).
- To investigate the potential of the resulting complexes as building blocks for coordination polymers and metal-organic frameworks (MOFs).
Main Methods:
- Synthesis of the tetranucleating ligand and its metal complexes.
- Metathesis reactions for metal ion substitution and ligand exchange.
- Single-crystal X-ray diffraction for structural elucidation.
- ESI mass spectrometry (ESI-MS), cyclic voltammetry (CV), and EPR spectroscopy for characterization.
Main Results:
- Isolation of a zinc chloride complex [Zn4(dbpbp)Cl4]2+ and its subsequent substitution with CuII, FeIII, and CoII/III.
- Formation of 2-D polymeric honeycomb sheets with [M4(dbpbp)Cl4]2+ (M = ZnII, CuII).
- Preparation of mixed-metal tetrabenzoate complexes and a cobalt-dioxygen adduct [Co4(dbpbp)(O2)2(O2CC6H5)2]4+ capable of reversible O2 binding.
Conclusions:
- The dbpbp2- ligand effectively coordinates four metal ions, enabling the formation of diverse multinuclear complexes.
- The characterized complexes serve as modules for constructing 1-D and 2-D coordination polymers and MOFs.
- The cobalt-dioxygen complex demonstrates potential for applications in reversible oxygen capture and storage.
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