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Mixed valency in a neutral 1D Fe-chloranilate coordination polymer
Katelyn M Clutterbuck1, Brendan F Abrahams1, Timothy A Hudson1
1School of Chemistry, University of Melbourne, Parkville, Victoria 3010, Australia. bfa@unimelb.edu.au.
Dalton Transactions (Cambridge, England : 2003)
|June 7, 2022
Summary
Researchers synthesized two iron-based coordination polymers. These materials exhibit different iron oxidation states and ligand properties, suggesting potential for electron transfer driven by π-π interactions.
Area of Science:
- Coordination Chemistry
- Materials Science
- Inorganic Chemistry
Background:
- Coordination polymers offer tunable properties based on metal centers and organic linkers.
- Anilate-based ligands provide versatile platforms for constructing complex structures.
Purpose of the Study:
- To synthesize and characterize novel one-dimensional (1D) iron-anilate coordination polymers.
- To investigate the structural and electronic properties of these materials, including oxidation states and ligand forms.
Main Methods:
- Synthesis of iron-anilate coordination polymers using specific ligands (3,6-difluoro-2,5-dihydroxy-1,4-benzoquinone and 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) and bridging molecules (4,4'-bipyridine and triphenylphosphine oxide).
- Structural analysis to determine the arrangement of metal centers and ligands in the 1D chains.
- Investigation of oxidation states of iron centers and anilate ligands under varying conditions.
Main Results:
- Two neutral 1D coordination polymers, Fe(Fan)(4,4'-bipy)2 and Fe(Clan)(OPPh3)2, were successfully synthesized.
- Fe(Fan)(4,4'-bipy)2 features Fe(II) centers and a dianionic Fan ligand.
- Fe(Clan)(OPPh3)2 exhibits near Fe(III) and chloranilate(-III) oxidation states at low temperatures, suggesting potential for electron transfer.
Conclusions:
- The study reports the synthesis and structural characterization of two distinct iron-anilate coordination polymers.
- Differences in oxidation states between the two compounds highlight the influence of ligand choice and temperature.
- Intrachain π-π interactions are proposed as a mechanism facilitating electron transfer from iron to bridging ligands.
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