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Anthryl-functionalized cyanide-bridged Fe/Co cubes
Qi Liu1, Yue Cheng1, Shihao Liu1
1Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China. chenzy@sustech.edu.cn.
Dalton Transactions (Cambridge, England : 2003)
|August 29, 2023
Summary
Two novel anthryl-functionalized cyanide-bridged iron-cobalt [Fe4Co4] cube complexes were synthesized. These complexes form distinct supramolecular chains and exhibit incomplete spin-crossover transitions near 200 K.
Area of Science:
- Coordination Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Cyanide-bridged metal complexes offer tunable properties through variations in metal ions and ligands.
- Anthracene functionalization can influence intermolecular interactions and solid-state assembly.
- Spin crossover (SCO) phenomena in iron complexes are of interest for molecular switches and sensors.
Purpose of the Study:
- To synthesize and characterize novel anthryl-functionalized cyanide-bridged [Fe4Co4] cube complexes.
- To investigate the supramolecular assembly and magnetic properties of these complexes.
- To explore the luminescence behavior and potential applications of the synthesized compounds.
Main Methods:
- Synthesis and single-crystal X-ray diffraction for structural elucidation of the [Fe4Co4] cubes.
- Magnetic susceptibility measurements to study spin crossover transitions.
- Luminescence spectroscopy to assess photophysical properties and aggregation effects.
Main Results:
- Two complexes, [(pzTp)Fe(CN)3Co(TpEtOAn)]4[OTf]4·8MeCN·7Et2O (1) and [NEt4]3[(pzTp)Fe(CN)3Co(TpEtOAn)]4[OTf]7·5MeCN·2Et2O (2), were successfully synthesized.
- Complex 1 forms linear supramolecular chains via anthryl-anthryl π-π stacking, while complex 2 exhibits a zigzag 1D assembly.
- Both compounds show incomplete SCO transitions from paramagnetic {FeIIILS(μ-CN)CoIIHS} to diamagnetic {FeIILS(μ-CN)CoIIILS} states around 200 K.
- Complex 1 displays enhanced luminescence upon dilution or addition of perfluoronaphthalene, indicating suppression of aggregation-caused quenching (ACQ).
Conclusions:
- The anthryl groups facilitate the formation of distinct supramolecular architectures in the solid state.
- The [Fe4Co4] cubes exhibit temperature-dependent spin crossover behavior.
- The luminescence properties suggest potential for applications where aggregation control is important, possibly related to ACQ effects.
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